Microbiocidal (e.g. fungicidal) 1,2,3-triazole derivatives

ABSTRACT

A compound of formula (I): 
     
       
         
         
             
             
         
       
     
     where A is an ortho-substituted ring selected from a number of specified rings;
     R 1  is halogen, cyano, nitro, C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy or C 1-4  haloalkoxy or optionally substituted C 2-4  alkenyl, optionally substituted C 2-4  alkynyl or optionally substituted SO 2 (C 1-4 )alkyl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4  alkoxy);   R 2  is C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy(C 1-4 )alkyl or C 1-4  alkylthio(C 1-4 )alkyl or [optionally substituted aryl](C 1-4 )alkyl- or [optionally substituted aryl]oxy(C 1-4 )alkyl-(where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4  alkoxy);   R 3  is hydrogen, CH 2 C≡CR 4 , CH 2 CR 4 ═C(H)R 4 , CH═C═CH 2  or COR 5  or optionally substituted C 1-4  alkyl, optionally substituted C 1-4  alkoxy or optionally substituted (C 1-4 ) alkylC(═O)O (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4  alkoxy, C 1-4  alkyl, C 1-2  haloalkoxy, hydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl and ethylsulfonyl);   each R 4  is, independently, hydrogen, halogen, C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy or C 1-4  alkoxy(C 1-4 )alkyl; and   R 5  is hydrogen or optionally substituted C 1-6  alkyl, optionally substituted C 1-4  alkoxy, optionally substituted C 1-4  alkoxy(C 1-4 )alkyl, optionally substituted C 1-4  alkylthio(C 1-4 )alkyl or optionally substituted aryl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, C 1-6  alkoxy, C 1-6  haloalkoxy, cyano, hydroxy, methoxycarbonyl and ethoxycarbonyl).

The present invention relates to novel 1,2,3-triazole derivatives which have microbiocidal activity, in particular fungicidal activity. The invention also relates to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

The present invention provides a compound of formula (I):

where A is an ortho-substituted ring selected from formulae (A1) to (A22);

Q is a single or a double bond; X is O, N(R¹⁸), S or (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n); R¹ is halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy or optionally substituted C₂₋₄ alkenyl, optionally substituted C₂₋₄ alkynyl or optionally substituted SO₂(C₁₋₄)alkyl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C₁₋₄ alkoxy); R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl or C₁₋₄ alkylthio(C₁₋₄)alkyl or [optionally substituted aryl](C₁₋₄)alkyl- or [optionally substituted aryl]oxy(C₁₋₄)alkyl-(where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C₁₋₄ alkoxy); R³ is hydrogen, CH₂C≡CR⁴, CH₂CR⁴═C(H)R⁴, CH═C═CH₂ or COR⁵ or optionally substituted C₁₋₄ alkyl, optionally substituted C₁₋₄ alkoxy or optionally substituted (C₁₋₄) alkylC(═O)O (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, C₁₋₄ alkoxy, C₁₋₄ alkyl, C₁₋₂ haloalkoxy, hydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl and ethylsulfonyl); each R⁴ is, independently, hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy or C₁₋₄ alkoxy(C₁₋₄)alkyl; R⁵ is hydrogen or optionally substituted C₁₋₆ alkyl, optionally substituted C₁₋₄ alkoxy, optionally substituted C₁₋₄ alkoxy(C₁₋₄)alkyl, optionally substituted C₁₋₄ alkylthio(C₁₋₄)alkyl or optionally substituted aryl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, cyano, hydroxy, methoxycarbonyl and ethoxycarbonyl); R⁶ is phenyl [optionally substituted by up to 3 substituents, each independently selected from halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ haloalkylthio, C(H)═N—OH, C(H)═N—O(C₁₋₆ alkyl), C(C₁₋₆ alkyl)═N—OH, C(C₁₋₆ alkyl)═N—O—(C₁₋₆ alkyl), (Z)_(p)C≡CR²⁵ and (Z)_(p)CR²⁸═CR²⁶R²⁷], a 5-6 membered heterocyclic ring [in which the ring contains 1 to 3 heteroatoms (each independently chosen from oxygen, sulphur and nitrogen) and the ring is optionally substituted by up to 3 substituents, each independently selected from halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C(H)═N—O—(C₁₋₆ alkyl) and C(C₁₋₆ alkyl)═N—O—(C₁₋₆ alkyl)], C₃₋₁₂ alkyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—C₁₋₄ alkyl, ═N—OH, ═N—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) and C₄₋₈ cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy)], C₂₋₁₂ alkenyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—(C₁₋₄ alkyl), ═N—OH, ═N—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) and C₄₋₈ cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy)], C₂₋₁₂ alkynyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—C₁₋₄ alkyl, ═N—OH, ═N—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy), Si(CH₃)₃ and C₄₋₈ cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy)], C₃₋₈ cycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₃₋₆ cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) and phenyl (itself optionally substituted by up to five independently selected halogen atoms)], C₄₋₈ cycloalkenyl [optionally substituted by up to 3 substituents, each independently selected from halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₃₋₆ cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) and phenyl (itself optionally substituted by up to five independently selected halogen atoms)], C₆₋₁₂ bicycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, C₁₋₄ alkyl and C₁₋₄ haloalkyl] or an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms]; R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are each, independently, hydrogen, halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl or C₁₋₄ thiohaloalkyl; R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each, independently, hydrogen, halogen, C₁₋₄ alkyl, C(O)CH₃, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₁₋₄ thiohaloalkyl, hydroxymethyl or C₁₋₄ alkoxymethyl; R¹⁸ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl, formyl, C(═O)C₁₋₄ alkyl (optionally substituted by halogen or C₁₋₄-alkoxy) or C(═O)O—C₁₋₆ alkyl (optionally substituted by halogen, C₁₋₄ alkoxy or CN); R¹⁹, R²⁰, R²¹, R²², R²³ and R²⁴ are each, independently, C₁₋₆ alkyl, C₁₋₆ alkenyl [both optionally substituted by halogen, hydroxy, ═O, C₁₋₄ alkoxy, O—C(O)—C₁₋₄ alkyl, aryl or a 3-7 membered carbocyclic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from nitrogen and oxygen), hydrogen, halogen, hydroxy or C₁₋₄ alkoxy; or R¹⁹R²⁰ together with the carbon atom to which they are attached form a carbonyl-group, a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups), C₁₋₆ alkylidene (optionally substituted by up to three methyl groups) or C₃₋₆ cycloalkylidene (optionally substituted by up to three methyl groups); R²⁵ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄haloalkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl, C₁₋₄haloalkoxy(C₁₋₄)alkyl or Si(C₁₋₄ alkyl)₃; R²⁶ and R²⁷ are each, independently, hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl; R²⁸ is hydrogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl; m is 0 or 1; n is 0 or 1; p is 0 or 1; and Z is C₁₋₄ alkylene.

Halogen is fluoro, chloro, bromo or iodo.

Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, neo-pentyl, n-heptyl, 1,3-dimethylbutyl, 1,3-dimethylpentyl, 1-methyl-3-ethyl-butyl or 1,3,3-trimethylbutyl.

Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF₃, CF₂Cl, CHF₂, CH₂F, CCl₃, CF₃CH₂, CHF₂CH₂, CH₂FCH₂, CH₃CHF or CH₃CF₂.

Alkenyl and alkynyl moieties can be in the form of straight or branched chains. The alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl, allyl, ethynyl and propargyl.

Alkylidene moieties can be in the form of straight or branched chains. Alkylidene includes methylidene [CH₂═C], ethylidene [CH₃C(H)═C], n-propylidene, i-propylidene [(CH₃)₂C═C], n-butylidene, i-butylidene, 2-butylidene, n-pentylidene, i-pentylidene, neo-pentylidene, 2-pentylidene, n-hexylidene, 2-hexylidene, 3-hexylidene, i-hexylidene and neo-hexylidene.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl.

Cycloalkylidene includes cyclopropylidene [c(C₃H₄)═C], cyclobutylidene, cyclopentylidene and cyclohexylidene.

Bicycloalkyl includes bicyclo[1,1,1]pentyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1]heptyl, bicyclo[2,2,2]octyl, bicyclo[3,2,1]octyl and bicyclo[3,2,2]nonyl.

Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but is preferably phenyl.

In one aspect of the invention, A is as defined above provided that it is not (A1).

In another aspect of the invention, R⁶ is as defined above provided that it is not an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms].

In a further aspect of the invention, A is as defined above provided that it is not (A1) when R⁶ is an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms].

Preferably Q is a single bond.

Preferably n is 0.

Preferably m is 0.

Preferably A is selected from formulae (A1), (A2), (A3), (A16), (A17), (A18), (A19), (A20) and (A22).

More preferably A is selected from formulae (A1), (A2), (A18), (A19) and (A22).

Even more preferably A is selected from one of the following ortho-substituted rings:

where R¹³ and R¹⁴ are each, independently, selected from H and C₁₋₄ alkyl.

Preferably X is O, NR¹⁸ or (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n).

More preferably X is O or (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n).

Even more preferably X is (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n).

Most preferably X is (CR¹⁹R²⁰).

Preferably R¹ is C₁₋₄ alkyl, C₁₋₄ haloalkyl, NO₂, CN or OCF₃.

More preferably R¹ is CHF₂, CF₃, CH₂F, CF₂Cl, CH₃ or C₂H₅.

Even more preferably R¹ is CHF₂, CF₃, CH₂F, CF₂C₁ or CH₃.

Most preferably R¹ is CHF₂, CF₃ or CH₂F.

Preferably R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl or C₁₋₄ alkylthio(C₁₋₄)alkyl.

More preferably R² is CH₃, CF₃, C₂H₅, CH₂OCH₃ or CH₂SCH₃.

Even more preferably R² is CH₃ or C₂H₅.

Most preferably R² is CH₃.

Preferably R³ is hydrogen, CH₂C≡CR⁴, CH₂CR⁴═C(H)R⁴, CH═C═CH₂ or COR⁵.

More preferably R³ is H, CH₂C≡CH, CH═C═CH₂, CH₂CH═CH₂ or COCH₃.

Still more preferably R³ is H, CH₂C≡CH, CH═C═CH₂ or CH₂CH═CH₂.

Even more preferably R³ is H, CH₂C≡CH or CH═C═CH₂.

Most preferably R³ is H.

Preferably each R⁴ is, independently, H, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy.

More preferably each R⁴ is, independently, H, Cl, Br, CH₃ or CH₃O.

Still more preferably each R⁴ is, independently, H, Cl or CH₃.

Most preferably each R⁴ is H.

Preferably R⁵ is H, C₁₋₆ alkyl, C₁₋₄ alkoxy or C₁₋₄ alkoxy(C₁₋₄)alkyl.

More preferably R⁵ is H, methyl, OC(CH₃)₃ or CH₂OCH₃.

Even more preferably R⁵ is H or methyl.

Preferably R⁶ is chosen from C₃₋₁₀ alkyl, C₃₋₉ haloalkyl, C₃₋₇ cycloalkyl [optionally substituted by C₃ cycloalkyl (itself optionally substituted by C₁₋₂ alkyl) or by up to two C₁₋₄ alkyl groups], an aliphatic group [which contains three to ten carbon atoms and at least one silicon atom and, optionally, one oxygen atom], thienyl [optionally substituted by halo], furyl [optionally substituted by halo], pyridyl [optionally substituted by halo], oxazolyl, isoxazolyl and

where R^(c) and R^(d) are, independently, H, Cl, Br, F, I, CN, NO₂, C₁₋₄ alkyl, CF₃, SCF₃, OCF₃, CH═NOH, CH═N—OC₁₋₆ alkyl, C≡CH, C≡C—Si(CH₃)₃, C(H)═CH₂ or C(H)═CH(C₁₋₄ alkyl).

More preferably R⁶ is C₃₋₇ alkyl, C₃₋₆ cycloalkyl [optionally substituted by C₁₋₄ alkyl or a C₃ cycloalkyl (itself optionally substituted by C₁₋₂ alkyl)], an aliphatic group (which contains three to eight carbon atoms and at least one silicon atom) or

where R^(e) is Cl, Br, F, CF₃, OCF₃, CH═N—OC₁₋₄ alkyl, C≡CH, C≡C—Si(CH₃)₃ or C(H)═CH₂ [in one aspect it is preferred that R^(e) is Cl, Br, F, CF₃, OCF₃, CH═N—OC₁₋₄ alkyl, C≡CH or C(H)═CH₂].

Even more preferably R⁶ is chosen from one of the following moieties:

where R^(e) is Cl, Br, F, CF₃, C≡CH, C≡C—Si(CH₃)₃ or CH═N—OC₁₋₄ alkyl [in one aspect it is preferred that R^(e) is Cl, Br, F, CF₃, C≡CH or CH═N—OC₁₋₄ alkyl].

Preferably R⁷ is H, F or CH₃.

Preferably R⁸ is H.

Preferably R⁹ is H.

Preferably R¹⁰ is H.

Preferably R¹¹ is H.

Preferably R¹² is H.

Preferably R¹³, R¹⁴, R¹⁵, R¹⁶ are each, independently, H, CH₃, C₂H₅, CF₃, CH₃O, C(O)CH₃ or CH₃OCH₂.

More preferably R¹³, R¹⁴, R¹⁵, R¹⁶ are each, independently, H or CH₃.

Preferably R¹⁷ is H.

Preferably R¹⁸ is H, CH₃, C₂H₅, C(O)OC₁₋₄ alkyl (optionally substituted with halogen or C₁₋₄ alkoxy) or COH.

More preferably R¹⁸ is C(O)OC₁₋₄ alkyl (optionally substituted with halogen or C₁₋₄ alkoxy) or COH.

Even more preferably R¹⁸ is C(O)OC₁₋₄ alkyl (optionally substituted with halogen or C₁₋₄ alkoxy).

Most preferably R¹⁸ is C(O)OC₁₋₄ alkyl.

Preferably R¹⁹ and R²⁰ are each, independently, H, halogen, C₁₋₅ alkyl, C₁₋₃ alkoxy, CH₂O, C₃₋₆ cycloalkyl, CH₂O—C(═O)CH₃, CH₂—C₃₋₆ cycloalkyl or benzyl; or R¹⁹ and R²⁰ together with the carbon atom to which they are attached form a carbonyl group, a 3-5 membered carbocyclic ring, C₁₋₅ alkylidene or C₃₋₆ cycloalkylidene.

More preferably R¹⁹ and R²⁰ are, independently, H, CH₃, C₂H₅, n-C₃H₇, i-C₃H₇, i-C₄H₉, CH(C₂H₅)₂, CH₂-cyclopropyl or cyclopentyl; or R¹⁹ and R²⁰ together with the carbon atom to which they are attached form a 3-membered carbocyclic ring.

Preferably R²¹ is H or CH₃.

Preferably R²² is H or CH₃.

Preferably R²³ is H or CH₃.

Preferably R²⁴ is H or CH₃.

Compounds of formula (II):

where R¹ and R² are as defined above for a compound of formula (I) and Y is halogen, hydroxy or C₁₋₅ alkoxy, are useful as intermediates in the preparation of compounds of formula (I).

Some compounds of formula (TI) are already known in the literature [B. Iddon et al. J. Chem. Soc. Perkin Trans. 1, 1341 (1996); M. Begtrup et al., Acta Chemica Scand., 19, 2022 (1965); D. R. Buckle et al., J. Chem. Res, Syn. 10, 292 (1982); and A. Peratoner et al., Sci. Fis. Mat. Nat. Rend 5, 16 (1907)] but others are novel.

Therefore, in another aspect the present invention provides a compound of formula (TI) where R¹ and R² are as defined above for a compound of formula (I) and Y is halogen, hydroxy or C₁₋₅ alkoxy; provided that when R¹ is chloro and R² is 4-CH₃O—C₆H₄—CH₂—, Y is not C₂H₅O; when R¹ is CH₃O and R² is CH₃, Y is not C₂H₅O; when R¹ is bromo and R² is CH₃OCH₂, Y is not CH₃O; and when R¹ is CH₃ and R² is C₂H₅, Y is not OH.

Preferably Y is hydroxy, chloro, fluoro or C₁₋₃ alkoxy.

Some compounds of formula (IIIa) are also novel but some are described in the literature [see, for example, L. A Paquette et al., J. Amer. Chem. Soc. 99, 3734 (1977); H. Plieninger et al., Chem. Ber. 109, 2121 (1976); Kasansski et al., Zh. Obshch. Khim. (1959), 29, 2588; and A. J. Kirby et al., J. Chem. Soc., Perkin Trans. 2, 1997, 1081].

Anilines of formula (IIIa) are novel when R¹³, R¹⁴, R¹⁵R¹⁶, Q and X are as defined above for a compound of formula (I); provided that when R¹³, R¹⁴, R¹⁵ and R¹⁶ are each H then X is not CH₂ when Q is a double bond and X is not CH₂CH₂ when Q is a single bond or a double bond; and when R¹³ is CH₃, R¹⁴ is OCH₃ and R¹⁵ and R¹⁶ are both H then X is not CH₂CH₂ when Q is a single bond.

Therefore, in a further aspect, the present invention provides a compound of formula (IIIa) where R¹³, R¹⁴, R¹⁵, R¹⁶, Q and X are as defined above for a compound of formula (I); provided that when R¹³, R¹⁴, R¹⁵ and R¹⁶ are each H then X is not CH₂ when Q is a double bond and X is not CH₂CH₂ when Q is a single bond or a double bond; and when R¹³ is CH₃, R¹⁴ is OCH₃ and R¹⁵ and R¹⁶ are both H then X is not CH₂CH₂ when Q is a single bond.

The compounds of formula (I), (II) and (IIIa) may exist as different geometric or optical isomers or in different tautomeric forms. This invention covers, for each formula, all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.

The compounds in Tables 1 to 28 below illustrate compounds of the invention.

Table 1 provides 59 compounds of formula (II) wherein R¹, R² and Y are as defined in Table 1.

TABLE 1 Compound Number R¹ R² Y 1.01 CHF₂ CH₃ OH 1.02 CHF₂ CH₃ Cl 1.03 CHF₂ CH₃ OCH₃ 1.04 CHF₂ CH₃ OC₂H₅ 1.05 CHF₂ CH₃ OC₃H₇(n) 1.06 CHF₂ CH₃ OC₃H₇(i) 1.07 CHF₂ C₂H₅ OH 1.08 CHF₂ C₂H₅ Cl 1.09 CHF₂ C₂H₅ OCH₃ 1.10 CHF₂ C₂H₅ OC₂H₅ 1.11 CHF₂ C₂H₅ OC₃H₇(n) 1.12 CHF₂ C₂H₅ OC₃H₇(i) 1.13 CF₃ CH₃ OH 1.14 CF₃ CH₃ Cl 1.15 CF₃ CH₃ OCH₃ 1.16 CF₃ CH₃ OC₂H₅ 1.17 CF₃ CH₃ OC₃H₇(n) 1.18 CF₃ CH₃ OC₃H₇(i) 1.19 CF₃ C₂H₅ OH 1.20 CF₃ C₂H₅ Cl 1.21 CF₃ C₂H₅ OCH₃ 1.22 CF₃ C₂H₅ OC₂H₅ 1.23 CF₃ C₂H₅ OC₃H₇(n) 1.24 CF₃ C₂H₅ OC₃H₇(i) 1.25 CF₃ CH₂OCH₃ OH 1.26 CF₃ CH₂OCH₃ Cl 1.27 CF₃ CH₂OCH₃ OCH₃ 1.28 CF₃ CH₂OCH₃ OC₂H₅ 1.29 CF₃ CH₂OCH₃ OC₃H₇(n) 1.30 CF₃ CH₂OCH₃ OC₃H₇(i) 1.31 CF₃ CH₃ F 1.32 CHF₂ CH₃ F 1.33 CHF₂ CH₂OCH₃ OH 1.34 CHF₂ CH₂OCH₃ OCH₃ 1.35 CHF₂ CH₂OCH₃ OC₂H₅ 1.36 CF₃ CH₂SCH₃ OH 1.37 CF₃ CH₂SCH₃ OCH₃ 1.38 CN CH₃ OCH₃ 1.39 OCF₃ CH₃ OCH₃ 1.40 NO₂ CH₃ OCH₃ 1.41 CH₃ CH₃ OH 1.42 CH₃ CH₃ OCH₃ 1.43 CH₃ CH₃ Cl 1.44 CH₃ C₂H₅ OH 1.45 C₂F₅ CH₃ OCH₃ 1.46 CF₃ CF₃ OCH₃ 1.47 CH₃ CF₃ OCH₃ 1.48 CH₂F CH₃ OH 1.49 CH₂F CH₃ Cl 1.50 CH₂F CH₃ OCH₃ 1.51 CH₂F CH₃ OC₂H₅ 1.52 CH₂F CH₃ OC₃H₇(n) 1.53 CH₂F CH₃ OC₃H₇(i) 1.54 CH₂F C₂H₅ OH 1.55 CH₂F C₂H₅ Cl 1.56 CH₂F C₂H₅ OCH₃ 1.57 CH₂F C₂H₅ OC₂H₅ 1.58 CH₂F C₂H₅ OC₃H₇(n) 1.59 CH₂F C₂H₅ OC₃H₇(i)

Table X represents Table 2 [when X is 2], Table 3 [when X is 3], Table 4 [when X is 4], Table 5 [when X is 5], Table 6 [when X is 6] and represents Table 7 [when X is 7].

TABLE X Cmpd. No. R² R³ R⁶ R⁷ X.001 CH₃ H phenyl H X.002 CH₃ CH₂C≡CH phenyl H X.003 CH₃ H 2′-fluorophenyl H X.004 CH₃ H 3′-fluorophenyl H X.005 CH₃ H 4′-fluorophenyl H X.006 C₂H₅ H 4′-fluorophenyl H X.007 CH₂OCH₃ H 4′-fluorophenyl H X.008 CH₃ COCH₃ 4′-fluorophenyl H X.009 CH₃ COCH₂OCH₃ 4′-fluorophenyl H X.010 CH₃ CH₂C≡CH 4′-fluorophenyl H X.011 CH₃ CH═C═CH₂ 4′-fluorophenyl H X.012 CH₃ COO-tert-Bu 4′-fluorophenyl H X.013 CH₃ H 4′-fluorophenyl F X.014 CH₃ H 4′-fluorophenyl CH₃ X.015 CH₃ H 2′-chlorophenyl H X.016 CH₃ H 3′-chlorophenyl H X.017 CH₃ H 4′-chlorophenyl H X.018 C₂H₅ H 4′-chlorophenyl H X.019 CH₂OCH₃ H 4′-chlorophenyl H X.020 CH₃ COCH₃ 4′-chlorophenyl H X.021 CH₃ COCH₂OCH₃ 4′-chlorophenyl H X.022 CH₃ CH₂C≡CH 4′-chlorophenyl H X.023 CH₃ CH═C═CH₂ 4′-chlorophenyl H X.024 CH₃ COO-tert-Bu 4′-chlorophenyl H X.025 CH₃ H 4′-chlorophenyl F X.026 CH₃ H 4′-chlorophenyl CH₃ X.027 CH₃ H 2′-bromophenyl H X.028 CH₃ H 3′-bromophenyl H X.029 CH₃ H 4′-bromophenyl H X.030 C₂H₅ H 4′-bromophenyl H X.031 CH₂OCH₃ H 4′-bromophenyl H X.032 CH₃ COCH₃ 4′-bromophenyl H X.033 CH₃ COCH₂OCH₃ 4′-bromophenyl H X.034 CH₃ CH₂C≡CH 4′-bromophenyl H X.035 CH₃ CH═C═CH₂ 4′-bromophenyl H X.036 CH₃ COO-tert-Bu 4′-bromophenyl H X.037 CH₃ H 4′-bromophenyl F X.038 CH₃ H 4′-bromophenyl CH₃ X.039 CH₃ H 2′-iodophenyl H X.040 CH₃ H 3′-iodophenyl H X.041 CH₃ H 4′-iodophenyl H X.042 CH₃ H 2′-CF₃-phenyl H X.043 CH₃ H 3′-CF₃-phenyl H X.044 CH₃ H 4′-CF₃-phenyl H X.045 C₂H₅ H 4′-CF₃-phenyl H X.046 CH₂OCH₃ H 4′-CF₃-phenyl H X.047 CH₃ COCH₃ 4′-CF₃-phenyl H X.048 CH₃ COCH₂OCH₃ 4′-CF₃-phenyl H X.049 CH₃ CH₂C≡CH 4′-CF₃-phenyl H X.050 CH₃ COO-tert-Bu 4′-CF₃-phenyl H X.051 CH₃ H 2′-OCF₃-phenyl H X.052 CH₃ H 3′-OCF₃-phenyl H X.053 CH₃ H 4′-OCF₃-phenyl H X.054 C₂H₅ H 4′-OCF₃-phenyl H X.055 CH₂OCH₃ H 4′-OCF₃-phenyl H X.056 CH₃ COCH₃ 4′-OCF₃-phenyl H X.057 CH₃ COCH₂OCH₃ 4′-OCF₃-phenyl H X.058 CH₃ CH₂C≡CH 4′-OCF₃-phenyl H X.059 CH₃ COO-tert-Bu 4′-OCF₃-phenyl H X.060 CH₃ CH═C═CH₂ 4′-OCF₃-phenyl H X.061 CH₃ H 4′-SCF₃-phenyl H X.062 CH₃ H 2′-CH═NOH-phenyl H X.063 CH₃ H 3′-CH═NOH-phenyl H X.064 CH₃ H 4′-CH═NOH-phenyl H X.065 CH₃ H 2′-CH═NOCH₃-phenyl H X.066 CH₃ H 3′-CH═NOCH₃-phenyl H X.067 CH₃ H 4′-CH═NOCH₃-phenyl H X.068 CH₃ H 2′-CH═NOC₂H₅-phenyl H X.069 CH₃ H 3′-CH═NOC₂H₅-phenyl H X.070 CH₃ H 4′-CH═NOC₂H₅-phenyl H X.071 CH₃ H 2′-CN-phenyl H X.072 CH₃ H 3′-CN-phenyl H X.073 CH₃ H 4′-CN-phenyl H X.074 CH₃ H 2′-NO₂-phenyl H X.075 CH₃ H 3′-NO₂-phenyl H X.076 CH₃ H 4′-NO₂-phenyl H X.077 CH₃ H 3′,4′-difluorophenyl H X.078 C₂H₅ H 3′,4′-difluorophenyl H X.079 CH₂OCH₃ H 3′,4′-difluorophenyl H X.080 CH₃ COCH₃ 3′,4′-difluorophenyl H X.081 CH₃ COCH₂OCH₃ 3′,4′-difluorophenyl H X.082 CH₃ CH₂C≡CH 3′,4′-difluorophenyl H X.083 CH₃ COO-tert-Bu 3′,4′-difluorophenyl H X.084 CH₃ CH═C═CH₂ 3′,4′-difluorophenyl H X.085 CH₃ H 3′,4′-difluorophenyl F X.086 CH₃ H 3′,4′-difluorophenyl CH₃ X.087 CH₃ H 3′,4′-dichlorophenyl H X.088 C₂H₅ H 3′,4′-dichlorophenyl H X.089 CH₂OCH₃ H 3′,4′-dichlorophenyl H X.090 CH₃ COCH₃ 3′,4′-dichlorophenyl H X.091 CH₃ COCH₂OCH₃ 3′,4′-dichlorophenyl H X.092 CH₃ CH₂C≡CH 3′,4′-dichlorophenyl H X.093 CH₃ COO-tert-Bu 3′,4′-dichlorophenyl H X.094 CH₃ CH═C═CH₂ 3′,4′-dichlorophenyl H X.095 CH₃ H 3′,4′-dichlorophenyl F X.096 CH₃ H 3′,4′-dichlorophenyl CH₃ X.097 CH₃ H 4′-chloro-3′-fluoro-phenyl H X.098 C₂H₅ H 4′-chloro-3′-fluoro-phenyl H X.099 CH₂OCH₃ H 4′-chloro-3′-fluoro-phenyl H X.100 CH₃ COCH₃ 4′-chloro-3′-fluoro-phenyl H X.101 CH₃ COCH₂OCH₃ 4′-chloro-3′-fluoro-phenyl H X.102 CH₃ CH₂C≡CH 4′-chloro-3′-fluoro-phenyl H X.103 CH₃ COO-tert-Bu 4′-chloro-3′-fluoro-phenyl H X.104 CH₃ CH═C═CH₂ 4′-chloro-3′-fluoro-phenyl H X.105 CH₃ H 4′-chloro-3′-fluoro-phenyl F X.106 CH₃ H 4′-chloro-3′-fluoro-phenyl CH₃ X.107 CH₃ H 3′-chloro-4′-fluoro-phenyl H X.108 C₂H₅ H 3′-chloro-4′-fluoro-phenyl H X.109 CH₂OCH₃ H 3′-chloro-4′-fluoro-phenyl H X.110 CH₃ COCH₃ 3′-chloro-4′-fluoro-phenyl H X.111 CH₃ COCH₂OCH₃ 3′-chloro-4′-fluoro-phenyl H X.112 CH₃ CH₂C≡CH 3′-chloro-4′-fluoro-phenyl H X.113 CH₃ COO-tert-Bu 3′-chloro-4′-fluoro-phenyl H X.114 CH₃ CH═C═CH₂ 3′-chloro-4′-fluoro-phenyl H X.115 CH₃ H 3′-chloro-4′-fluoro-phenyl F X.116 CH₃ H 3′-chloro-4′-fluoro-phenyl CH₃ X.117 CH₃ H 2′-4′-dichloro-phenyl H X.118 CH₂OCH₃ H 2′-4′-dichloro-phenyl H X.119 CH₃ H 2′-4′-difluoro-phenyl H X.120 CH₂OCH₃ H 2′-4′-difluoro-phenyl H X.121 CH₃ H CH₂CH₂CH₃ H X.122 C₂H₅ H CH₂CH₂CH₃ H X.123 CH₂OCH₃ H CH₂CH₂CH₃ H X.124 CH₃ CH₂C≡CH CH₂CH₂CH₃ H X.125 CH₃ H CH₂CH₂CH₂CH₃ H X.126 C₂H₅ H CH₂CH₂CH₂CH₃ H X.127 CH₂OCH₃ H CH₂CH₂CH₂CH₃ H X.128 CH₃ CH₂C≡CH CH₂CH₂CH₂CH₃ H X.129 CH₃ H CH₂CH₂CH₂CH₃ F X.130 CH₃ H CH₂CH₂CH₂CH₃ CH₃ X.131 CH₃ H CH₂CH₂CH₂(C₂H₅) H X.132 C₂H₅ H CH₂CH₂CH₂(C₂H₅) H X.133 CH₂OCH₃ H CH₂CH₂CH₂(C₂H₅) H X.134 CH₃ CH₂C≡CH CH₂CH₂CH₂(C₂H₅) H X.135 CH₃ H CH₂CH₂CH₂(C₂H₅) F X.136 CH₃ H CH₂CH₂CH₂(C₂H₅) CH₃ X.137 CH₃ H CH₂CH₂CH(CH₃)₂ H X.138 C₂H₅ H CH₂CH₂CH(CH₃)₂ H X.139 CH₂OCH₃ H CH₂CH₂CH(CH₃)₂ H X.140 CH₃ COCH₃ CH₂CH₂CH(CH₃)₂ H X.141 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)₂ H X.142 CH₃ CH₂C≡CH CH₂CH₂CH(CH₃)₂ H X.143 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)₂ H X.144 CH₃ CH═C═CH₂ CH₂CH₂CH(CH₃)₂ H X.145 CH₃ H CH₂CH₂CH(CH₃)₂ F X.146 CH₃ H CH₂CH₂CH(CH₃)₂ CH₃ X.147 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) H X.148 C₂H₅ H CH₂CH₂CH(CH₃)(C₂H₅) H X.149 CH₂OCH₃ H CH₂CH₂CH(CH₃)(C₂H₅) H X.150 CH₃ COCH₃ CH₂CH₂CH(CH₃)(C₂H₅) H X.151 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)(C₂H₅) H X.152 CH₃ CH₂C≡CH CH₂CH₂CH(CH₃)(C₂H₅) H X.153 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)(C₂H₅) H X.154 CH₃ CH═C═CH₂ CH₂CH₂CH(CH₃)(C₂H₅) H X.155 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) F X.156 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) CH₃ X.157 CH₃ H CH₂CH₂CH(C₂H₅)₂ H X.158 C₂H₅ H CH₂CH₂CH(C₂H₅)₂ H X.159 CH₂OCH₃ H CH₂CH₂CH(C₂H₅)₂ H X.160 CH₃ COCH₃ CH₂CH₂CH(C₂H₅)₂ H X.161 CH₃ COCH₂OCH₃ CH₂CH₂CH(C₂H₅)₂ H X.162 CH₃ CH₂C≡CH CH₂CH₂CH(C₂H₅)₂ H X.163 CH₃ COO-tert-Bu CH₂CH₂CH(C₂H₅)₂ H X.164 CH₃ CH═C═CH₂ CH₂CH₂CH(C₂H₅)₂ H X.165 CH₃ H CH₂CH₂CH(C₂H₅)₂ F X.166 CH₃ H CH₂CH₂CH(C₂H₅)₂ CH₃ X.167 CH₃ H CH₂CH₂C(CH₃)₃ H X.168 C₂H₅ H CH₂CH₂C(CH₃)₃ H X.169 CH₂OCH₃ H CH₂CH₂C(CH₃)₃ H X.170 CH₃ COCH₃ CH₂CH₂C(CH₃)₃ H X.171 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)₃ H X.172 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₃ H X.173 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)₃ H X.174 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)₃ H X.175 CH₃ H CH₂CH₂C(CH₃)₃ F X.176 CH₃ H CH₂CH₂C(CH₃)₃ CH₃ X.177 CH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) H X.178 C₂H₅ H CH₂CH₂C(CH₃)₂(C₂H₅) H X.179 CH₂OCH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) H X.180 CH₃ COCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) H X.181 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) H X.182 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₂(C₂H₅) H X.183 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)₂(C₂H₅) H X.184 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)₂(C₂H₅) H X.185 CH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) F X.186 CH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) CH₃ X.187 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ H X.188 C₂H₅ H CH₂CH₂C(CH₃)(C₂H₅)₂ H X.189 CH₂OCH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ H X.190 CH₃ COCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ H X.191 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ H X.192 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)(C₂H₅)₂ H X.193 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)(C₂H₅)₂ H X.194 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)(C₂H₅)₂ H X.195 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ F X.196 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ CH₃ X.197 CH₃ H CH(CH₃)CH₂CH₃ H X.198 C₂H₅ H CH(CH₃)CH₂CH₃ H X.199 CH₂OCH₃ H CH(CH₃)CH₂CH₃ H X.200 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₃ H X.201 CH₃ H CH(C₂H₅)CH₂CH₃ H X.202 C₂H₅ H CH(C₂H₅)CH₂CH₃ H X.203 CH₂OCH₃ H CH(C₂H₅)CH₂CH₃ H X.204 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₃ H X.205 CH₃ H CH(CF₃)CH₂CH₃ H X.206 C₂H₅ H CH(CF₃)CH₂CH₃ H X.207 CH₂OCH₃ H CH(CF₃)CH₂CH₃ H X.208 CH₃ CH₂C≡CH CH(CF₃)CH₂CH₃ H X.209 CH₃ H CH(CH₃)CH₂CH₂CH₃ H X.210 C₂H₅ H CH(CH₃)CH₂CH₂CH₃ H X.211 CH₂OCH₃ H CH(CH₃)CH₂CH₂CH₃ H X.212 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₂CH₃ H X.213 CH₃ H CH(C₂H₅)CH₂CH₂CH₃ H X.214 C₂H₅ H CH(C₂H₅)CH₂CH₂CH₃ H X.215 CH₂OCH₃ H CH(C₂H₅)CH₂CH₂CH₃ H X.216 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₂CH₃ H X.217 CH₃ H CH(CF₃)CH₂CH₂CH₃ H X.218 C₂H₅ H CH(CF₃)CH₂CH₂CH₃ H X.219 CH₃ H CH(CH₃)CH₂CH(CH₃)₂ H X.220 C₂H₅ H CH(CH₃)CH₂CH(CH₃)₂ H X.221 CH₂OCH₃ H CH(CH₃)CH₂CH(CH₃)₂ H X.222 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)₂ H X.223 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)₂ H X.224 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)₂ H X.225 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)₂ H X.226 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(CH₃)₂ H X.227 CH₃ H CH(CH₃)CH₂CH(CH₃)₂ F X.228 CH₃ H CH(CH₃)CH₂CH(CH₃)₂ CH₃ X.229 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.230 C₂H₅ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.231 CH₂OCH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.232 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.233 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.234 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.235 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.236 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.237 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) F X.238 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) CH₃ X.239 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ H X.240 C₂H₅ H CH(CH₃)CH₂CH(C₂H₅)₂ H X.241 CH₂OCH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ H X.242 CH₃ COCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ H X.243 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ H X.244 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(C₂H₅)₂ H X.245 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(C₂H₅)₂ H X.246 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(C₂H₅)₂ H X.247 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ F X.248 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ CH₃ X.249 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ H X.250 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)₂ H X.251 CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ H X.252 CH₃ COCH₃ CH(C₂H₅)CH₂CH(CH₃)₂ H X.253 CH₃ COCH₂OCH₃ CH(C₂H₅)CH₂CH(CH₃)₂ H X.254 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(CH₃)₂ H X.255 CH₃ COO-tert-Bu CH(C₂H₅)CH₂CH(CH₃)₂ H X.256 CH₃ CH═C═CH₂ CH(C₂H₅)CH₂CH(CH₃)₂ H X.257 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ F X.258 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ CH₃ X.259 CH₃ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.260 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.261 CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.262 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.263 CH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.264 C₂H₅ H CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.265 CH₂OCH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.266 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.267 CH₃ H CH(CF₃)CH₂CH(CH₃)₂ H X.268 C₂H₅ H CH(CF₃)CH₂CH(CH₃)₂ H X.269 CH₂OCH₃ H CH(CF₃)CH₂CH(CH₃)₂ H X.270 CH₃ CH₂C≡CH CH(CF₃)CH₂CH(CH₃)₂ H X.271 CH₃ H CH(CF₃)CH₂CH(CH₃)(C₂H₅) H X.272 CH₃ H CH(CF₃)CH₂CH(C₂H₅)₂ H X.273 CH₃ H CH(CH₃)CH₂C(CH₃)₃ H X.274 C₂H₅ H CH(CH₃)CH₂C(CH₃)₃ H X.275 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₃ H X.276 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₃ H X.277 CH₃ COCH₂OCH₃ CH(CH₃)CH₂C(CH₃)₃ H X.278 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₃ H X.279 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₃ H X.280 CH₃ CH═C═CH₂ CH(CH₃)CH₂C(CH₃)₃ H X.281 CH₃ H CH(CH₃)CH₂C(CH₃)₃ F X.282 CH₃ H CH(CH₃)CH₂C(CH₃)₃ CH₃ X.283 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.284 C₂H₅ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.285 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.286 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.287 CH₃ COCH₂OCH₃ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.288 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.289 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.290 CH₃ CH═C═CH₂ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.291 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) F X.292 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) CH₃ X.293 CH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ H X.294 C₂H₅ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ H X.295 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ H X.296 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ H X.297 CH₃ H CH(C₂H₅)CH₂C(CH₃)₃ H X.298 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₃ H X.299 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₃ H X.300 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₃ H X.301 CH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.302 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.303 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.304 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.305 CH₃ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.306 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.307 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.308 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.309 CH₃ H CH(CF₃)CH₂C(CH₃)₃ H X.310 C₂H₅ H CH(CF₃)CH₂C(CH₃)₃ H X.311 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₃ H X.312 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)₃ H X.313 CH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.314 C₂H₅ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.315 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.316 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.317 CH₃ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.318 C₂H₅ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.319 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.320 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.321 CH₃ H 2′-tert-butyl-cyclopropyl H X.322 C₂H₅ H 2′-tert-butyl-cyclopropyl H X.323 CH₂OCH₃ H 2′-tert-butyl-cyclopropyl H X.324 CH₃ CH₂C≡CH 2′-tert-butyl-cyclopropyl H X.325 CH₃ H 2′-isobutyl-cyclopropyl H X.326 C₂H₅ H 2′-isobutyl-cyclopropyl H X.327 CH₂OCH₃ H 2′-isobutyl-cyclopropyl H X.328 CH₃ CH₂C≡CH 2′-isobutyl-cyclopropyl H X.329 CH₃ H 4′,4′-dimethyl-cyclobutyl H X.330 C₂H₅ H 4′,4′-dimethyl-cyclobutyl H X.331 CH₂OCH₃ H 4′,4′-dimethyl-cyclobutyl H X.332 CH₃ CH₂C≡CH 4′,4′-dimethyl-cyclobutyl H X.333 CH₃ H cyclopentyl H X.334 C₂H₅ H cyclopentyl H X.335 CH₂OCH₃ H cyclopentyl H X.336 CH₃ CH₂C≡CH cyclopentyl H X.337 CH₃ H 3′-methyl-cyclopentyl H X.338 C₂H₅ H 3′-methyl-cyclopentyl H X.339 CH₂OCH₃ H 3′-methyl-cyclopentyl H X.340 CH₃ CH₂C≡CH 3′-methyl-cyclopentyl H X.341 CH₃ H cyclohexyl H X.342 C₂H₅ H cyclohexyl H X.343 CH₂OCH₃ H cyclohexyl H X.344 CH₃ CH₂C≡CH cyclohexyl H X.345 CH₃ H 3′-methyl-cyclohexyl H X.346 C₂H₅ H 3′-methyl-cyclohexyl H X.347 CH₂OCH₃ H 3′-methyl-cyclohexyl H X.348 CH₃ CH₂C≡CH 3′-methyl-cyclohexyl H X.349 CH₃ H 4′-methyl-cyclohexyl H X.350 C₂H₅ H 4′-methyl-cyclohexyl H X.351 CH₂OCH₃ H 4′-methyl-cyclohexyl H X.352 CH₃ CH₂C≡CH 4′-methyl-cyclohexyl H X.353 CH₃ H cycloheptyl H X.354 C₂H₅ H cycloheptyl H X.355 CH₂OCH₃ H cycloheptyl H X.356 CH₃ CH₂C≡CH cycloheptyl H X.357 CH₃ H 2′-thienyl H X.358 C₂H₅ H 2′-thienyl H X.359 CH₂OCH₃ H 2′-thienyl H X.360 CH₃ CH₂C≡CH 2′-thienyl H X.361 CH₃ H 3′-thienyl H X.362 C₂H₅ H 3′-thienyl H X.363 CH₂OCH₃ H 3′-thienyl H X.364 CH₃ CH₂C≡CH 3′-thienyl H X.365 CH₃ H 5′-chloro-2′-thienyl H X.366 C₂H₅ H 5′-chloro-2′-thienyl H X.367 CH₂OCH₃ H 5′-chloro-2′-thienyl H X.368 CH₃ CH₂C≡CH 5′-chloro-2′-thienyl H X.369 CH₃ H 2′-furyl H X.370 C₂H₅ H 2′-furyl H X.371 CH₂OCH₃ H 2′-furyl H X.372 CH₃ CH₂C≡CH 2′-furyl H X.373 CH₃ H 5′-chloro-2′-furyl H X.374 C₂H₅ H 5′-chloro-2′-furyl H X.375 CH₂OCH₃ H 5′-chloro-2′-furyl H X.376 CH₃ CH₂C≡CH 5′-chloro-2′-furyl H X.377 CH₃ H 2′-pyridyl H X.378 C₂H₅ H 2′-pyridyl H X.379 CH₂OCH₃ H 2′-pyridyl H X.380 CH₃ CH₂C≡CH 2′-pyridyl H X.381 CH₃ H 3′-pyridyl H X.382 C₂H₅ H 3′-pyridyl H X.383 CH₂OCH₃ H 3′-pyridyl H X.384 CH₃ CH₂C≡CH 3′-pyridyl H X.385 CH₃ H 4′-pyridyl H X.386 C₂H₅ H 4′-pyridyl H X.387 CH₂OCH₃ H 4′-pyridyl H X.388 CH₃ CH₂C≡CH 4′-pyridyl H X.389 CH₃ H 6′-chloro-3′-pyridyl H X.390 C₂H₅ H 6′-chloro-3′-pyridyl H X.391 CH₂OCH₃ H 6′-chloro-3′-pyridyl H X.392 CH₃ CH₂C≡CH 6′-chloro-3′-pyridyl H X.393 CH₃ H 6′-fluoro-3′-pyridyl H X.394 C₂H₅ H 6′-fluoro-3′-pyridyl H X.395 CH₂OCH₃ H 6′-fluoro-3′-pyridyl H X.396 CH₃ CH₂C≡CH 6′-fluoro-3′-pyridyl H X.397 CH₃ H 6′-bromo-3′-pyridyl H X.398 C₂H₅ H 6′-bromo-3′-pyridyl H X.399 CH₂OCH₃ H 6′-bromo-3′-pyridyl H X.400 CH₃ CH₂C≡CH 6′-bromo-3′-pyridyl H X.401 CH₃ H 2′-oxazolyl H X.402 CH₃ H 3′-isoxazolyl H X.403 CH₃ H CH(CH₃)₂ H X.404 C₂H₅ H CH(CH₃)₂ H X.405 CH₂OCH₃ H CH(CH₃)₂ H X.406 CH₃ CH₂C≡CH CH(CH₃)₂ H X.407 CH₃ H 4′-CH═NO(n)-C₄H₉-phenyl H X.408 CH₃ H 4′-CH═NO(iso)-C₄H₉-phenyl H X.409 CH₃ H 4′-CH═NO(iso)-C₃H₇-phenyl H X.410 CH₃ H 4′-CH═NO(n)-C₃H₇-phenyl H X.411 CH₃ H Si(CH₃)₃ H X.412 C₂H₅ H Si(CH₃)₃ H X.413 CH₂OCH₃ H Si(CH₃)₃ H X.414 CH3 CH₂C≡CH Si(CH₃)₃ H X.415 CH₃ H CH₂Si(CH₃)₃ H X.416 C₂H₅ H CH₂Si(CH₃)₃ H X.416 CH₂OCH₃ H CH₂Si(CH₃)₃ H X.418 CH3 CH₂C≡CH CH₂Si(CH₃)₃ H X.419 CH₃ H CH(CH₃)Si(CH₃)₃ H X.420 C₂H₅ H CH(CH₃)Si(CH₃)₃ H X.421 CH₂OCH₃ H CH(CH₃)Si(CH₃)₃ H X.422 CH3 CH₂C≡CH CH(CH₃)Si(CH₃)₃ H X.423 CH₃ H CH₂CH₂Si(CH₃)₃ H X.424 C₂H₅ H CH₂CH₂Si(CH₃)₃ H X.425 CH₂OCH₃ H CH₂CH₂Si(CH₃)₃ H X.426 CH3 CH₂C≡CH CH₂CH₂Si(CH₃)₃ H X.427 CH₃ H CH(CH₃)CH₂Si(CH₃)₃ H X.428 C₂H₅ H CH(CH₃)CH₂Si(CH₃)₃ H X.429 CH₂OCH₃ H CH(CH₃)CH₂Si(CH₃)₃ H X.430 CH3 CH₂C≡CH CH(CH₃)CH₂Si(CH₃)₃ H X.431 CH₃ H CH₂CH₂CH₂Si(CH₃)₃ H X.432 C₂H₅ H CH₂CH₂CH₂Si(CH₃)₃ H X.433 CH₂OCH₃ H CH₂CH₂CH₂Si(CH₃)₃ H X.434 CH3 CH₂C≡CH CH₂CH₂CH₂Si(CH₃)₃ H X.435 CH₃ H CH₂Si(CH₃)₂C₂H₅ H X.436 CH₃ H CH₂Si(CH₃)₂CH(CH₃)₂ H X.437 CH₃ H CH₂Si(CH₃)₂OCH₃ H X.438 CH₃ H CH₂CH₂Si(CH₃)₂OCH₃ H X.439 CH₃ H CH(CH₃)Si(CH₃)₂OCH₃ H X.440 CH₃ H CH(CH₃)CH₂Si(CH₃)₂OCH₃ H X.441 CH₃ H 2′-cyclopropyl-cyclopropyl H X.442 C₂H₅ H 2′-cyclopropyl-cyclopropyl H X.443 CH₂OCH₃ H 2′-cyclopropyl-cyclopropyl H X.444 CH₃ CH₂C≡CH 2′-cyclopropyl-cyclopropyl H X.445 CH₃ H 2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.446 C₂H₅ H 2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.447 CH₂OCH₃ H 2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.448 CH₃ CH₂C≡CH 2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.449 CH₃ H 2′-cyclobutyl-cyclopropyl H X.450 CH₃ H 2′-cyclopentyl-cyclopropyl H X.451 CH₃ H 2′-cyclohexyl-cyclopropyl H X.452 CH₃ H 4′-C≡CH-phenyl H X.453 C₂H₅ H 4′-C≡CH-phenyl H X.454 CH₃ H 4′-C≡C—Si(CH₃)₃-phenyl H X.455 C₂H₅ H 4′-C≡C—Si(CH₃)₃-phenyl H X.456 CH₃ H 4′-C(H)═CH₂-phenyl H X.457 C₂H₅ H 4′-C(H)═CH₂-phenyl H

Table 2 provides 457 compounds of formula (I-2):

wherein R², R³, R⁶ and R⁷ are as defined in Table 2.

Table 3 provides 457 compounds of formula (I-3):

wherein R², R³, R⁶ and R⁷ are as defined in Table 3.

Table 4 provides 457 compounds of formula (I-4):

wherein R², R³, R⁶ and R⁷ are as defined in Table 4.

Table 5 provides 457 compounds of formula (I-5):

wherein R², R³, R⁶ and R⁷ are as defined in Table 5.

Table 6 provides 457 compounds of formula (I-6):

wherein R², R³, R⁶ and R⁷ are as defined in Table 6.

Table 7 provides 457 compounds of formula (I-7):

wherein R², R³, R⁶ and R⁷ are as defined in Table 7.

Table Y represents Table 8 [when Y is 8], Table 9 [when Y is 9], Table 10 [when Y is 10], Table 11 [when Y is 11], Table 12 [when Y is 12], Table 13 [when Y is 13], Table 14 [when Y is 14], Table 15 [when Y is 15], Table 16 [when Y is 16], Table 17 [when Y is 17], Table 18 [when Y is 18] and represents Table 19 [when Y is 19].

TABLE Y Com- pound No. R² R³ R⁶ Y.001 CH₃ H phenyl Y.002 CH₃ CH₂C≡CH phenyl Y.003 CH₃ H 2′-fluorophenyl Y.004 CH₃ H 3′-fluorophenyl Y.005 CH₃ H 4′-fluorophenyl Y.006 C₂H₅ H 4′-fluorophenyl Y.007 CH₂OCH₃ H 4′-fluorophenyl Y.008 CH₃ COCH₃ 4′-fluorophenyl Y.009 CH₃ COCH₂OCH₃ 4′-fluorophenyl Y.010 CH₃ CH₂C≡CH 4′-fluorophenyl Y.011 CH₃ CH═C═CH₂ 4′-fluorophenyl Y.012 CH₃ COO-tert-Bu 4′-fluorophenyl Y.013 CH₃ H 2′-chlorophenyl Y.014 CH₃ H 3′-chlorophenyl Y.015 CH₃ H 4′-chlorophenyl Y.016 C₂H₅ H 4′-chlorophenyl Y.017 CH₂OCH₃ H 4′-chlorophenyl Y.018 CH₃ COCH₃ 4′-chlorophenyl Y.019 CH₃ COCH₂OCH₃ 4′-chlorophenyl Y.020 CH₃ CH₂C≡CH 4′-chlorophenyl Y.021 CH₃ CH═C═CH₂ 4′-chlorophenyl Y.022 CH₃ COO-tert-Bu 4′-chlorophenyl Y.023 CH₃ H 2′-bromophenyl Y.024 CH₃ H 3′-bromophenyl Y.025 CH₃ H 4′-bromophenyl Y.026 C₂H₅ H 4′-bromophenyl Y.027 CH₂OCH₃ H 4′-bromophenyl Y.028 CH₃ COCH₃ 4′-bromophenyl Y.029 CH₃ COCH₂OCH₃ 4′-bromophenyl Y.030 CH₃ CH₂C≡CH 4′-bromophenyl Y.031 CH₃ CH═C═CH₂ 4′-bromophenyl Y.032 CH₃ COO-tert-Bu 4′-bromophenyl Y.033 CH₃ H 2′-iodophenyl Y.034 CH₃ H 3′-iodophenyl Y.035 CH₃ H 4′-iodophenyl Y.036 CH₃ H 2′-CF₃-phenyl Y.037 CH₃ H 3′-CF₃-phenyl Y.038 CH₃ H 4′-CF₃-phenyl Y.039 C₂H₅ H 4′-CF₃-phenyl Y.040 CH₂OCH₃ H 4′-CF₃-phenyl Y.041 CH₃ COCH₃ 4′-CF₃-phenyl Y.042 CH₃ COCH₂OCH₃ 4′-CF₃-phenyl Y.043 CH₃ CH₂C≡CH 4′-CF₃-phenyl Y.044 CH₃ COO-tert-Bu 4′-CF₃-phenyl Y.045 CH₃ H 2′-OCF₃-phenyl Y.046 CH₃ H 3′-OCF₃-phenyl Y.047 CH₃ H 4′-OCF₃-phenyl Y.048 C₂H₅ H 4′-OCF₃-phenyl Y.049 CH₂OCH₃ H 4′-OCF₃-phenyl Y.050 CH₃ COCH₃ 4′-OCF₃-phenyl Y.051 CH₃ COCH₂OCH₃ 4′-OCF₃-phenyl Y.052 CH₃ CH₂C≡CH 4′-OCF₃-phenyl Y.053 CH₃ COO-tert-Bu 4′-OCF₃-phenyl Y.054 CH₃ CH═C═CH₂ 4′-OCF₃-phenyl Y.055 CH₃ H 4′-SCF₃-phenyl Y.056 CH₃ H 2′-CH═NOH-phenyl Y.057 CH₃ H 3′-CH═NOH-phenyl Y.058 CH₃ H 4′-CH═NOH-phenyl Y.059 CH₃ H 2′-CH═NOCH₃-phenyl Y.060 CH₃ H 3′-CH═NOCH₃-phenyl Y.061 CH₃ H 4′-CH═NOCH₃-phenyl Y.062 CH₃ H 2′-CH═NOC₂H₅-phenyl Y.063 CH₃ H 3′-CH═NOC₂H₅-phenyl Y.064 CH₃ H 4′-CH═NOC₂H₅-phenyl Y.065 CH₃ H 2′-CN-phenyl Y.066 CH₃ H 3′-CN-phenyl Y.067 CH₃ H 4′-CN-phenyl Y.068 CH₃ H 2′-NO₂-phenyl Y.069 CH₃ H 3′-NO₂-phenyl Y.070 CH₃ H 4′-NO₂-phenyl Y.071 CH₃ H 3′,4′-difluorophenyl Y.072 C₂H₅ H 3′,4′-difluorophenyl Y.073 CH₂OCH₃ H 3′,4′-difluorophenyl Y.074 CH₃ COCH₃ 3′,4′-difluorophenyl Y.075 CH₃ COCH₂OCH₃ 3′,4′-difluorophenyl Y.076 CH₃ CH₂C≡CH 3′,4′-difluorophenyl Y.077 CH₃ COO-tert-Bu 3′,4′-difluorophenyl Y.078 CH₃ CH═C═CH₂ 3′,4′-difluorophenyl Y.079 CH₃ H 3′,4′-dichlorophenyl Y.080 C₂H₅ H 3′,4′-dichlorophenyl Y.081 CH₂OCH₃ H 3′,4′-dichlorophenyl Y.082 CH₃ COCH₃ 3′,4′-dichlorophenyl Y.083 CH₃ COCH₂OCH₃ 3′,4′-dichlorophenyl Y.084 CH₃ CH₂C≡CH 3′,4′-dichlorophenyl Y.085 CH₃ COO-tert-Bu 3′,4′-dichlorophenyl Y.086 CH₃ CH═C═CH₂ 3′,4′-dichlorophenyl Y.087 CH₃ H 4′-chloro-3′-fluoro-phenyl Y.088 C₂H₅ H 4′-chloro-3′-fluoro-phenyl Y.089 CH₂OCH₃ H 4′-chloro-3′-fluoro-phenyl Y.090 CH₃ COCH₃ 4′-chloro-3′-fluoro-phenyl Y.091 CH₃ COCH₂OCH₃ 4′-chloro-3′-fluoro-phenyl Y.092 CH₃ CH₂C≡CH 4′-chloro-3′-fluoro-phenyl Y.093 CH₃ COO-tert-Bu 4′-chloro-3′-fluoro-phenyl Y.094 CH₃ CH═C═CH₂ 4′-chloro-3′-fluoro-phenyl Y.095 CH₃ H 3′-chloro-4′-fluoro-phenyl Y.096 C₂H₅ H 3′-chloro-4′-fluoro-phenyl Y.097 CH₂OCH₃ H 3′-chloro-4′-fluoro-phenyl Y.098 CH₃ COCH₃ 3′-chloro-4′-fluoro-phenyl Y.099 CH₃ COCH₂OCH₃ 3′-chloro-4′-fluoro-phenyl Y.100 CH₃ CH₂C≡CH 3′-chloro-4′-fluoro-phenyl Y.101 CH₃ COO-tert-Bu 3′-chloro-4′-fluoro-phenyl Y.102 CH₃ CH═C═CH₂ 3′-chloro-4′-fluoro-phenyl Y.103 CH₃ H 2′-4′-dichloro-phenyl Y.104 CH₂OCH₃ H 2′-4′-dichloro-phenyl Y.105 CH₃ H 2′-4′-difluoro-phenyl Y.106 CH₂OCH₃ H 2′-4′-difluoro-phenyl Y.107 CH₃ H CH₂CH₂CH₃ Y.108 C₂H₅ H CH₂CH₂CH₃ Y.109 CH₂OCH₃ H CH₂CH₂CH₃ Y.110 CH₃ CH₂C≡CH CH₂CH₂CH₃ Y.111 CH₃ H CH₂CH₂CH₂CH₃ Y.112 C₂H₅ H CH₂CH₂CH₂CH₃ Y.113 CH₂OCH₃ H CH₂CH₂CH₂CH₃ Y.114 CH₃ CH₂C≡CH CH₂CH₂CH₂CH₃ Y.115 CH₃ H CH₂CH₂CH₂(C₂H₅) Y.116 C₂H₅ H CH₂CH₂CH₂(C₂H₅) Y.117 CH₂OCH₃ H CH₂CH₂CH₂(C₂H₅) Y.118 CH₃ CH₂C≡CH CH₂CH₂CH₂(C₂H₅) Y.119 CH₃ H CH₂CH₂CH(CH₃)₂ Y.120 C₂H₅ H CH₂CH₂CH(CH₃)₂ Y.121 CH₂OCH₃ H CH₂CH₂CH(CH₃)₂ Y.122 CH₃ COCH₃ CH₂CH₂CH(CH₃)₂ Y.123 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)₂ Y.124 CH₃ CH₂C≡CH CH₂CH₂CH(CH₃)₂ Y.125 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)₂ Y.126 CH₃ CH═C═CH₂ CH₂CH₂CH(CH₃)₂ Y.127 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) Y.128 C₂H₅ H CH₂CH₂CH(CH₃)(C₂H₅) Y.129 CH₂OCH₃ H CH₂CH₂CH(CH₃)(C₂H₅) Y.130 CH₃ COCH₃ CH₂CH₂CH(CH₃)(C₂H₅) Y.131 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)(C₂H₅) Y.132 CH₃ CH₂C≡CH CH₂CH₂CH(CH₃)(C₂H₅) Y.133 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)(C₂H₅) Y.134 CH₃ CH═C═CH₂ CH₂CH₂CH(CH₃)(C₂H₅) Y.135 CH₃ H CH₂CH₂CH(C₂H₅)₂ Y.136 C₂H₅ H CH₂CH₂CH(C₂H₅)₂ Y.137 CH₂OCH₃ H CH₂CH₂CH(C₂H₅)₂ Y.138 CH₃ COCH₃ CH₂CH₂CH(C₂H₅)₂ Y.139 CH₃ COCH₂OCH₃ CH₂CH₂CH(C₂H₅)₂ Y.140 CH₃ CH₂C≡CH CH₂CH₂CH(C₂H₅)₂ Y.141 CH₃ COO-tert-Bu CH₂CH₂CH(C₂H₅)₂ Y.142 CH₃ CH═C═CH₂ CH₂CH₂CH(C₂H₅)₂ Y.143 CH₃ H CH₂CH₂C(CH₃)₃ Y.144 C₂H₅ H CH₂CH₂C(CH₃)₃ Y.145 CH₂OCH₃ H CH₂CH₂C(CH₃)₃ Y.146 CH₃ COCH₃ CH₂CH₂C(CH₃)₃ Y.147 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)₃ Y.148 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₃ Y.149 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)₃ Y.150 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)₃ Y.151 CH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) Y.152 C₂H₅ H CH₂CH₂C(CH₃)₂(C₂H₅) Y.153 CH₂OCH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) Y.154 CH₃ COCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) Y.155 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) Y.156 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₂(C₂H₅) Y.157 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)₂(C₂H₅) Y.158 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)₂(C₂H₅) Y.159 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ Y.160 C₂H₅ H CH₂CH₂C(CH₃)(C₂H₅)₂ Y.161 CH₂OCH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ Y.162 CH₃ COCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ Y.163 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ Y.164 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)(C₂H₅)₂ Y.165 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)(C₂H₅)₂ Y.166 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)(C₂H₅)₂ Y.167 CH₃ H CH(CH₃)CH₂CH₃ Y.168 C₂H₅ H CH(CH₃)CH₂CH₃ Y.169 CH₂OCH₃ H CH(CH₃)CH₂CH₃ Y.170 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₃ Y.171 CH₃ H CH(C₂H₅)CH₂CH₃ Y.172 C₂H₅ H CH(C₂H₅)CH₂CH₃ Y.173 CH₂OCH₃ H CH(C₂H₅)CH₂CH₃ Y.174 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₃ Y.175 CH₃ H CH(CF₃)CH₂CH₃ Y.176 C₂H₅ H CH(CF₃)CH₂CH₃ Y.177 CH₂OCH₃ H CH(CF₃)CH₂CH₃ Y.178 CH₃ CH₂C≡CH CH(CF₃)CH₂CH₃ Y.179 CH₃ H CH(CH₃)CH₂CH₂CH₃ Y.180 C₂H₅ H CH(CH₃)CH₂CH₂CH₃ Y.181 CH₂OCH₃ H CH(CH₃)CH₂CH₂CH₃ Y.182 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₂CH₃ Y.183 CH₃ H CH(C₂H₅)CH₂CH₂CH₃ Y.184 C₂H₅ H CH(C₂H₅)CH₂CH₂CH₃ Y.185 CH₂OCH₃ H CH(C₂H₅)CH₂CH₂CH₃ Y.186 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₂CH₃ Y.187 CH₃ H CH(CF₃)CH₂CH₂CH₃ Y.188 C₂H₅ H CH(CF₃)CH₂CH₂CH₃ Y.189 CH₃ H CH(CH₃)CH₂CH(CH₃)₂ Y.190 C₂H₅ H CH(CH₃)CH₂CH(CH₃)₂ Y.191 CH₂OCH₃ H CH(CH₃)CH₂CH(CH₃)₂ Y.192 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)₂ Y.193 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)₂ Y.194 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)₂ Y.195 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)₂ Y.196 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(CH₃)₂ Y.197 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.198 C₂H₅ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.199 CH₂OCH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.200 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.201 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.202 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.203 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.204 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.205 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ Y.206 C₂H₅ H CH(CH₃)CH₂CH(C₂H₅)₂ Y.207 CH₂OCH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ Y.208 CH₃ COCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ Y.209 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ Y.210 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(C₂H₅)₂ Y.211 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(C₂H₅)₂ Y.212 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(C₂H₅)₂ Y.213 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ Y.214 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)₂ Y.215 CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ Y.216 CH₃ COCH₃ CH(C₂H₅)CH₂CH(CH₃)₂ Y.217 CH₃ COCH₂OCH₃ CH(C₂H₅)CH₂CH(CH₃)₂ Y.218 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(CH₃)₂ Y.219 CH₃ COO-tert-Bu CH(C₂H₅)CH₂CH(CH₃)₂ Y.220 CH₃ CH═C═CH₂ CH(C₂H₅)CH₂CH(CH₃)₂ Y.221 CH₃ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.222 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.223 CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.224 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.225 CH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.226 C₂H₅ H CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.227 CH₂OCH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.228 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.229 CH₃ H CH(CF₃)CH₂CH(CH₃)₂ Y.230 C₂H₅ H CH(CF₃)CH₂CH(CH₃)₂ Y.231 CH₂OCH₃ H CH(CF₃)CH₂CH(CH₃)₂ Y.232 CH₃ CH₂C≡CH CH(CF₃)CH₂CH(CH₃)₂ Y.233 CH₃ H CH(CF₃)CH₂CH(CH₃)(C₂H₅) Y.234 CH₃ H CH(CF₃)CH₂CH(C₂H₅)₂ Y.235 CH₃ H CH(CH₃)CH₂C(CH₃)₃ Y.236 C₂H₅ H CH(CH₃)CH₂C(CH₃)₃ Y.237 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₃ Y.238 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₃ Y.239 CH₃ COCH₂OCH₃ CH(CH₃)CH₂C(CH₃)₃ Y.240 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₃ Y.241 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₃ Y.242 CH₃ CH═C═CH₂ CH(CH₃)CH₂C(CH₃)₃ Y.243 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.244 C₂H₅ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.245 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.246 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.247 CH₃ COCH₂OCH₃ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.248 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.249 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.250 CH₃ CH═C═CH₂ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.251 CH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.252 C₂H₅ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.253 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.254 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.255 CH₃ H CH(C₂H₅)CH₂C(CH₃)₃ Y.256 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₃ Y.257 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₃ Y.258 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₃ Y.259 CH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.260 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.261 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.262 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.263 CH₃ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.264 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.265 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.266 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.267 CH₃ H CH(CF₃)CH₂C(CH₃)₃ Y.268 C₂H₅ H CH(CF₃)CH₂C(CH₃)₃ Y.269 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₃ Y.270 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)₃ Y.271 CH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.272 C₂H₅ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.273 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.274 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.275 CH₃ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.276 C₂H₅ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.277 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.278 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.279 CH₃ H 2′-tert-butyl-cyclopropyl Y.280 C₂H₅ H 2′-tert-butyl-cyclopropyl Y.281 CH₂OCH₃ H 2′-tert-butyl-cyclopropyl Y.282 CH₃ CH₂C≡CH 2′-tert-butyl-cyclopropyl Y.283 CH₃ H 2′-isobutyl-cyclopropyl Y.284 C₂H₅ H 2′-isobutyl-cyclopropyl Y.285 CH₂OCH₃ H 2′-isobutyl-cyclopropyl Y.286 CH₃ CH₂C≡CH 2′-isobutyl-cyclopropyl Y.287 CH₃ H 4′,4′-dimethyl-cyclobutyl Y.288 C₂H₅ H 4′,4′-dimethyl-cyclobutyl Y.289 CH₂OCH₃ H 4′,4′-dimethyl-cyclobutyl Y.290 CH₃ CH₂C≡CH 4′,4′-dimethyl-cyclobutyl Y.291 CH₃ H cyclopentyl Y.292 C₂H₅ H cyclopentyl Y.293 CH₂OCH₃ H cyclopentyl Y.294 CH₃ CH₂C≡CH cyclopentyl Y.295 CH₃ H 3′-methyl-cyclopentyl Y.296 C₂H₅ H 3′-methyl-cyclopentyl Y.297 CH₂OCH₃ H 3′-methyl-cyclopentyl Y.298 CH₃ CH₂C≡CH 3′-methyl-cyclopentyl Y.299 CH₃ H cyclohexyl Y.300 C₂H₅ H cyclohexyl Y.301 CH₂OCH₃ H cyclohexyl Y.302 CH₃ CH₂C≡CH cyclohexyl Y.303 CH₃ H 3′-methyl-cyclohexyl Y.304 C₂H₅ H 3′-methyl-cyclohexyl Y.305 CH₂OCH₃ H 3′-methyl-cyclohexyl Y.306 CH₃ CH₂C≡CH 3′-methyl-cyclohexyl Y.307 CH₃ H 4′-methyl-cyclohexyl Y.308 C₂H₅ H 4′-methyl-cyclohexyl Y.309 CH₂OCH₃ H 4′-methyl-cyclohexyl Y.310 CH₃ CH₂C≡CH 4′-methyl-cyclohexyl Y.311 CH₃ H cycloheptyl Y.312 C₂H₅ H cycloheptyl Y.313 CH₂OCH₃ H cycloheptyl Y.314 CH₃ CH₂C≡CH cycloheptyl Y.315 CH₃ H 2′-thienyl Y.316 C₂H₅ H 2′-thienyl Y.317 CH₂OCH₃ H 2′-thienyl Y.318 CH₃ CH₂C≡CH 2′-thienyl Y.319 CH₃ H 3′-thienyl Y.320 C₂H₅ H 3′-thienyl Y.321 CH₂OCH₃ H 3′-thienyl Y.322 CH₃ CH₂C≡CH 3′-thienyl Y.323 CH₃ H 5′-chloro-2′-thienyl Y.324 C₂H₅ H 5′-chloro-2′-thienyl Y.325 CH₂OCH₃ H 5′-chloro-2′-thienyl Y.326 CH₃ CH₂C≡CH 5′-chloro-2′-thienyl Y.327 CH₃ H 2′-furyl Y.328 C₂H₅ H 2′-furyl Y.329 CH₂OCH₃ H 2′-furyl Y.330 CH₃ CH₂C≡CH 2′-furyl Y.331 CH₃ H 5′-chloro-2′-furyl Y.332 C₂H₅ H 5′-chloro-2′-furyl Y.333 CH₂OCH₃ H 5′-chloro-2′-furyl Y.334 CH₃ CH₂C≡CH 5′-chloro-2′-furyl Y.335 CH₃ H 2′-pyridyl Y.336 C₂H₅ H 2′-pyridyl Y.337 CH₂OCH₃ H 2′-pyridyl Y.338 CH₃ CH₂C≡CH 2′-pyridyl Y.339 CH₃ H 3′-pyridyl Y.340 C₂H₅ H 3′-pyridyl Y.341 CH₂OCH₃ H 3′-pyridyl Y.342 CH₃ CH₂C≡CH 3′-pyridyl Y.343 CH₃ H 4′-pyridyl Y.344 C₂H₅ H 4′-pyridyl Y.345 CH₂OCH₃ H 4′-pyridyl Y.346 CH₃ CH₂C≡CH 4′-pyridyl Y.347 CH₃ H 6′-chloro-3′-pyridyl Y.348 C₂H₅ H 6′-chloro-3′-pyridyl Y.349 CH₂OCH₃ H 6′-chloro-3′-pyridyl Y.350 CH₃ CH₂C≡CH 6′-chloro-3′-pyridyl Y.351 CH₃ H 6′-fluoro-3′-pyridyl Y.352 C₂H₅ H 6′-fluoro-3′-pyridyl Y.353 CH₂OCH₃ H 6′-fluoro-3′-pyridyl Y.354 CH₃ CH₂C≡CH 6′-fluoro-3′-pyridyl Y.355 CH₃ H 6′-bromo-3′-pyridyl Y.356 C₂H₅ H 6′-bromo-3′-pyridyl Y.357 CH₂OCH₃ H 6′-bromo-3′-pyridyl Y.358 CH₃ CH₂C≡CH 6′-bromo-3′-pyridyl Y.359 CH₃ H 2′-oxazolyl Y.360 CH₃ H 3′-isoxazolyl Y.361 CH₃ H CH(CH₃)₂ Y.362 C₂H₅ H CH(CH₃)₂ Y.363 CH₂OCH₃ H CH(CH₃)₂ Y.364 CH₃ CH₂C≡CH CH(CH₃)₂

Table 8 provides 364 compounds of formula (I-8):

wherein R², R³, and R⁶ are as defined in Table 8.

Table 9 provides 364 compounds of formula (I-9):

wherein R², R³, and R⁶ are as defined in Table 9.

Table 10 provides 364 compounds of formula (I-10):

wherein R², R³, and R⁶ are as defined in Table 10.

Table 11 provides 364 compounds of formula (I-11):

wherein R², R³, and R⁶ are as defined in Table 11.

Table 12 provides 364 compounds of formula (I-12):

wherein R², R³, and R⁶ are as defined in Table 12.

Table 13 provides 364 compounds of formula (I-13):

wherein R², R³, and R⁶ are as defined in Table 13.

Table 14 provides 364 compounds of formula (I-14):

wherein R², R³, and R⁶ are as defined in Table 14.

Table 15 provides 364 compounds of formula (I-15):

wherein R², R³, and R⁶ are as defined in Table 15.

Table 16 provides 364 compounds of formula (I-16):

wherein R², R³, and R⁶ are as defined in Table 16.

Table 17 provides 364 compounds of formula (I-17):

wherein R², R³, and R⁶ are as defined in Table 17.

Table 18 provides 364 compounds of formula (I-18):

wherein R², R³, and R⁶ are as defined in Table 18.

Table 19 provides 364 compounds of formula (I-19):

wherein R², R³, and R⁶ are as defined in Table 19.

Table Z represents Table 20 [when Z is 20], Table 21 [when Z is 21], Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is 24] and represents Table 25 [when Z is 25].

TABLE Z Compound No. R² R³ A Z.001 CH₃ H

Z.002 C₂H₅ H

Z.003 CH₂OCH₃ H

Z.004 CH₃ CH₂C≡CH

Z.005 CH₃ H

Z.006 C₂H₅ H

Z.007 CH₂OCH₃ H

Z.008 CH₃ CH₂C≡CH

Z.009 CH₃ H

Z.010 C₂H₅ H

Z.011 CH₂OCH₃ H

Z.012 CH₃ CH₂C≡CH

Z.013 CH₃ H

Z.014 C₂H₅ H

Z.015 CH₂OCH₃ H

Z.016 CH₃ CH₂C≡CH

Z.017 CH₃ H

Z.018 C₂H₅ H

Z.019 CH₂OCH₃ H

Z.020 CH₃ CH₂C≡CH

Z.021 CH₃ H

Z.022 C₂H₅ H

Z.023 CH₂OCH₃ H

Z.024 CH₃ CH₂C≡CH

Z.025 CH₃ H

Z.026 C₂H₅ H

Z.027 CH₂OCH₃ H

Z.028 CH₃ CH₂C≡CH

Z.029 CH₃ H

Z.030 C₂H₅ H

Z.031 CH₂OCH₃ H

Z.032 CH₃ CH₂C≡CH

Z.033 CH₃ H

Z.034 C₂H₅ H

Z.035 CH₂OCH₃ H

Z.036 CH₃ CH₂C≡CH

Z.037 CH₃ H

Z.038 C₂H₅ H

Z.039 CH₂OCH₃ H

Z.040 CH₃ CH₂C≡CH

Z.041 CH₃ H

Z.042 C₂H₅ H

Z.043 CH₂OCH₃ H

Z.044 CH₃ CH₂C≡CH

Z.045 CH₃ H

Z.046 C₂H₅ H

Z.047 CH₂OCH₃ H

Z.048 CH₃ CH₂C≡CH

Z.049 CH₃ H

Z.050 C₂H₅ H

Z.051 CH₂OCH₃ H

Z.052 CH₃ CH₂C≡CH

Z.053 CH₃ H

Z.054 C₂H₅ H

Z.055 CH₂OCH₃ H

Z.056 CH₃ CH₂C≡CH

Z.057 CH₃ H

Z.058 C₂H₅ H

Z.059 CH₂OCH₃ H

Z.060 CH₃ CH₂C≡CH

Z.061 CH₃ H

Z.062 C₂H₅ H

Z.063 CH₂OCH₃ H

Z.064 CH₃ CH₂C≡CH

Z.065 CH₃ H

Z.066 C₂H₅ H

Z.067 CH₂OCH₃ H

Z.068 CH₃ CH₂C≡CH

Z.069 CH₃ H

Z.070 C₂H₅ H

Z.071 CH₂OCH₃ H

Z.072 CH₃ CH₂C≡CH

Z.073 CH₃ H

Z.074 C₂H₅ H

Z.075 CH₂OCH₃ H

Z.076 CH₃ CH₂C≡CH

Z.077 CH₃ H

Z.078 C₂H₅ H

Z.079 CH₂OCH₃ H

Z.080 CH₃ CH₂C≡CH

Z.081 CH₃ H

Z.082 C₂H₅ H

Z.083 CH₂OCH₃ H

Z.084 CH₃ CH₂C≡CH

Z.085 CH₃ H

Z.086 C₂H₅ H

Z.087 CH₂OCH₃ H

Z.088 CH₃ CH₂C≡CH

Z.089 CH₃ H

Z.090 C₂H₅ H

Z.091 CH₂OCH₃ H

Z.092 CH₃ CH₂C≡CH

Z.093 CH₃ H

Z.094 C₂H₅ H

Z.095 CH₂OCH₃ H

Z.096 CH₃ CH₂C≡CH

Z.097 CH₃ H

Z.098 C₂H₅ H

Z.099 CH₂OCH₃ H

Z.100 CH₃ CH₂C≡CH

Z.101 CH₃ H

Z.102 C₂H₅ H

Z.103 CH₂OCH₃ H

Z.104 CH₃ CH₂C≡CH

Z.105 CH₃ H

Z.106 CH₃ H

Z.107 CH₃ H

Z.108 CH₃ H

Z.109 CH₃ H

Z.110 CH₃ H

Z.111 CH₃ H

Z.112 CH₃ H

Z.113 CH₃ H

Z.114 CH₃ H

Z.115 CH₃ H

Z.116 C₂H₅ H

Z.117 CH₂OCH₃ H

Z.118 CH₃ CH₂C≡CH

Z.119 CH₃ H

Z.120 CH₃ H

Z.121 C₂H₅ H

Z.122 CH₂OCH₃ H

Z.123 CH₃ CH₂C≡CH

Z.124 CH₃ H

Z.125 CH₃ H

Z.126 CH₃ H

Z.127 CH₃ H

Z.128 CH₃ H

Z.129 CH₃ H

Z.130 CH₃ H

Z.131 CH₃ H

Z.132 C₂H₅ H

Z.133 CH₂OCH₃ H

Z.134 CH₃ CH₂C≡CH

Z.135 CH₃ H

Z.136 CH₃ H

Z.137 C₂H₅ H

Z.138 CH₂OCH₃ H

Z.139 CH₃ CH₂C≡CH

Z.140 CH₃ H

Z.141 CH₃ H

Z.142 CH₃ H

Z.143 CH₃ H

Z.144 CH₃ H

Z.145 CH₃ H

Z.146 CH₃ H

Z.147 CH₃ H

Z.148 CH₃ H

Z.149 CH₃ H

Z.150 CH₃ H

Z.151 CH₃ H

Z.152 CH₃ H

Z.153 CH₃ H

Z.154 CH₃ H

Z.155 CH₃ H

Z.156 CH₃ H

Z.157 CH₃ H

Z.158 CH₃ H

Z.159 CH₃ H

Z.160 CH₃ H

Z.161 CH₃ H

Z.162 CH₃ H

Z.163 CH₃ H

Z.164 CH₃ H

Z.165 CH₃ H

Z.166 CH₃ H

Z.167 CH₃ H

Z.168 CH₃ H

Z.169 CH₃ H

Z.170 CH₃ H

Z.171 CH₃ H

Z.172 CH₃ H

Z.173 CH₃ H

Z.174 CH₃ H

Z.175 CH₃ H

Z.176 CH₃ H

Z.177 CH₃ H

Z.178 CH₃ H

Z.179 CH₃ H

Z.180 CH₃ H

Z.181 CH₃ H

Z.182 CH₃ H

Table 20 provides 182 compounds of formula (I-20):

wherein R², R³ and A are as defined in Table 20.

Table 21 provides 182 compounds of formula (I-21):

wherein R², R³ and A are as defined in Table 21.

Table 22 provides 182 compounds of formula (I-22):

wherein R², R³ and A are as defined in Table 22.

Table 23 provides 182 compounds of formula (I-23):

wherein R², R³ and A are as defined in Table 23.

Table 24 provides 182 compounds of formula (I-24):

wherein R², R³ and A are as defined in Table 24.

Table 25 provides 182 compounds of formula (I-25):

wherein R², R³ and A are as defined in Table 25.

Table 26 provides 133 compounds of formula (IIIa) where R¹³, R¹⁴, R¹⁵, R¹⁶, Q and X are as defined in Table 26. Q is shown to be either a single bond (—) or a double bond (═).

TABLE 26 Compound. No. R¹³ R¹⁴ R¹⁵ R¹⁶ Q X 26.001 CH₃ CH₃ H H ═ O 26.002 CH₃ H H H ═ O 26.003 H CH₃ H H ═ O 26.004 CH₃ CH₃ C(O)CH₃ H ═ O 26.005 CH₃ CH₃ H C(O)CH₃ ═ O 26.006 CH₃ C(O)CH₃ H H ═ O 26.007 H H H H ═ O 26.008 CF₃ CF₃ H H ═ O 26.009 OCH₃ OCH₃ H H ═ O 26.010 H H CH₃ CH₃ ═ O 26.011 C₂H₅ C₂H₅ H H ═ O 26.012 CH₃ H CH₃ H ═ O 26.013 H CH₃ H CH₃ ═ O 26.014 CH₃ CH₃ H H — O 26.015 CH₃ H H H — O 26.016 H CH₃ H H — O 26.017 CH₃ CH₃ C(O)CH₃ H — O 26.018 CH₃ CH₃ H C(O)CH₃ — O 26.019 CH₃ C(O)CH₃ H H — O 26.020 H H H H — O 26.021 CF₃ CF₃ H H — O 26.022 OCH₃ OCH₃ H H — O 26.023 H H CH₃ CH₃ — O 26.024 C₂H₅ C₂H₅ H H — O 26.025 CH₃ H CH₃ H — O 26.026 H H H H — CH₂ 26.027 CH₃ H CH₃ H — CH₂ 26.028 CH₃ H CH₃ H ═ CH₂ 26.029 H CH₃ H CH₃ — CH₂ 26.030 H CH₃ H CH₃ ═ CH₂ 26.031 CH₃ CH₃ CH₃ CH₃ ═ CH₂ 26.032 CH₃ CH₃ CH₃ CH₃ — CH₂ 26.033 CH₃ CH₃ CH₃ CH₃ ═ CH(CH₃) syn or anti 26.034 CH₃ CH₃ CH₃ CH₃ — CH(CH₃) syn or anti 26.035 H H H H ═ CH(CH₃) syn or anti 26.036 H H H H — CH(CH₃) syn or anti 26.037 H H H H — CH(C₂H₅) syn or anti 26.038 H H H H — CH₂CH₂ 26.039 CH₃ CH₃ H H ═ CH₂CH₂ 26.040 CH₃ CH₃ H H — CH₂CH₂ 26.041 H H CH₃ CH₃ ═ CH₂CH₂ 26.042 H H CH₃ CH₃ — CH₂CH₂ 26.043 H H OCH₃ H — CH₂CH₂ 26.044 H H H OCH₃ — CH₂CH₂ 26.045 H H H H — CH₂CH₂CH₂ 26.046 H H H H ═ CH₂CH₂CH₂ 26.047 H H CH₃ CH₃ ═ C(CH₃)₂ 26.048 H H CH₃ CH₃ — C(CH₃)₂ 26.049 CH₃ CH₃ CH₃ CH₃ ═ C(CH₃)₂ 26.050 CH₃ CH₃ CH₃ CH₃ — C(CH₃)₂ 26.051 CH₃ H CH₃ H — C(CH₃)₂ 26.052 H CH₃ H CH₃ — C(CH₃)₂ 26.053 CH₃ H CH₃ H ═ C(CH₃)₂ 26.054 H CH₃ H CH₃ ═ C(CH₃)₂ 26.055 CH₃ CH₃ CH₃ CH₃ — C(CH₃)(C₂H₅) 26.056 H H H H — C(CH₃)₂ 26.057 H H H H ═ C(CH₃)₂ 26.058 CH₃ CH₃ H H — C(CH₃)₂ 26.059 CH₃ CH₃ H H ═ C(CH₃)₂ 26.060 H H H H ═ C(OCH₃)₂ 26.061 H H H H — CH(OCH₃) 26.062 H H H H ═ S 26.063 H H H H — S 26.064 CH₃ CH₃ H H ═ S 26.065 CH₃ CH₃ H H — S 26.066 H H CH₃ CH₃ ═ S 26.067 H H CH₃ CH₃ — S 26.068 OCH₃ OCH₃ H H ═ S 26.069 OCH₃ OCH₃ H H — S 26.070 H CH₃ H H ═ S 26.071 H CH₃ H H — S 26.072 CH₃ H H H ═ S 26.073 CH₃ H H H — S 26.074 CH₃ H CH₃ H ═ S 26.075 CH₃ H CH₃ H — S 26.076 H CH₃ H CH₃ ═ S 26.077 H CH₃ H CH₃ — S 26.078 H OCH₃ H H ═ S 26.079 H OCH₃ H H — S 26.080 OCH₃ H H H ═ S 26.081 OCH₃ H H H — S 26.082 CH₃ H CH₃ CH₃ ═ S 26.083 CH₃ H CH₃ CH₃ — S 26.084 H CH₃ CH₃ CH₃ ═ S 26.085 H CH₃ CH₃ CH₃ — S 26.086 H H CH₃ H ═ S 26.087 H H CH₃ H — S 26.088 H H H CH₃ ═ S 26.089 H H H CH₃ — S 26.090 H H OCH₃ H ═ S 26.091 H H OCH₃ H — S 26.092 H H H OCH₃ ═ S 26.093 H H H OCH₃ — S 26.094 H H H H ═ N(CH₃) 26.095 H H H H — N(CH₃) 26.096 CH₃ CH₃ H H ═ N(CH₃) 26.097 CH₃ CH₃ H H — N(CH₃) 26.098 H H H H ═ N(C₂H₅) 26.099 H H H H — N(C₂H₅) 26.100 H H H H — NH 26.101 H H H H — NC(O)OC(CH₃)₃ 26.102 CH₃ CH₃ H H — NC(O)OC(CH₃)₃ 26.103 H H H H — N(CHO) 26.104 H H H H — N(C(O)CH₃) 26.105 CH₃ CH₃ H H — N(C(O)CH₃ 26.106 H H H H — N(C(O)OCH₃) 26.107 CH₃ CH₃ H H — N(C(O)OCH₃) 26.108 H H H H — N(C(O)OC₂H₅) 26.109 CH₃ CH₃ H H — N(C(O)OC₂H₅) 26.110 H H H H — N(C(O)OCH₂CH₂Cl) 26.111 CH₃ CH₃ H H — N(C(O)OCH₂CH₂Cl) 26.112 H H H H — N(C(O)OC₄H₉-(n) 26.113 CH₃ CH₃ H H — N(C(O)OC₄H₉-(n) 26.114 H H H H — N(C(O)OC₄H₉-(i) 26.115 CH₃ CH₃ H H — N(C(O)OC₄H₉-(i) 26.116 H H H H — CH(C₃H₇-(i)) syn or anti 26.117 H H H H — CH(C₃H₇-(n)) syn or anti 26.118 H H H H — CH(C₄H₉-(i)) syn or anti 26.119 H H H H — C(C₂H₄-(c)) 26.120 H H H H — C(C₄H₈-(c)) 26.121 H H H H — CHCH(C₂H₅)₂ syn or anti 26.122 H H H H — CHCH₂(C₃H₅-(c)) syn or anti 26.123 H H H H — CH(C₅H₉-(c)) syn or anti 26.124 H H H H — CHCH₂OC(═O)CH₃ syn or anti 26.125 H H H H — CH(CH═O) syn or anti 26.126 H H H H — CHCH₂OH 26.127 H H H H — C(OC₃H₇-(n))₂ 26.128 H H H H — C═O 26.129 H H H H — CHCH₂—C₆H₅ syn or anti 26.130 H H H H — C═C(CH₃)₂ 26.131 H H H H — C═C(C₂H5)₂ 26.132 H H H H — cyclopentylidene 26.133 H H H H — C(CH₃)(C₂H₅) In either configuration

Table ZZ represents Table 27 (when ZZ is 27) and represents Table 28 (when ZZ is 28).

TABLE ZZ Compound No. R³ R⁶ R² R¹ ZZ.1 H SiMe₃ Me CF₃ ZZ.2 H SiMe₃ Me CF₂H ZZ.3 H CH₂SiMe₃ Me CF₃ ZZ.4 H CH₂SiMe₃ Me CF₂H ZZ.5 propargyl CH₂SiMe₃ Me CF₃ ZZ.6 H CHMeSiMe₃ Me CF₃ ZZ.7 H CHMeSiMe₃ Me CF₂H ZZ.8 propargyl CHMeSiMe₃ Me CF₃ ZZ.9 allenyl CHMeSiMe₃ Me CF₃ ZZ.10 COMe CHMeSiMe₃ Me CF₃ ZZ.11 H CHMeSiMe₃ Me Me ZZ.12 H (CH₂)₂SiMe₃ Me CF₃ ZZ.13 H (CH₂)₂SiMe₃ Me CF₂H ZZ.14 propargyl (CH₂)₂SiMe₃ Me CF₃ ZZ.15 H (CH₂)₂SiMe₃ Me Me ZZ.16 H (CH₂)₂SiMe₃ CF₃ CF₃ ZZ.17 H CHMeCH₂SiMe₃ Me CF₃ ZZ.18 H CHMeCH₂SiMe₃ Me CF₂H ZZ.19 propargyl CHMeCH₂SiMe₃ Me CF₃ ZZ.20 propargyl CHMeCH₂SiMe₃ Me CF₂H ZZ.21 H CHMeCH₂SiMe₃ Me Me ZZ.22 H CHMeCH₂SiMe₃ CF₃ CF₃ ZZ.23 COMe CHMeCH₂SiMe₃ Me CF₃ ZZ.24 H (CH₂)₃SiMe₃ Me CF₃ ZZ.25 H (CH₂)₃SiMe₃ Me CF₂H ZZ.26 H CH₂Si(Me₂)Et Me CF₃ ZZ.27 H CH₂Si(Me₂)Et Me CF₂H ZZ.28 H CH₂Si(Me₂)CHMe₂ Me CF₃ ZZ.29 H CH₂Si(Me₂)CHMe₂ Me CF₂H ZZ.30 H CH₂CHMeSiMe₃ Me CF₃ ZZ.31 H CH₂CHMeSiMe₃ Me CF₂H ZZ.32 H CMe₂CH₂SiMe₃ Me CF₃ ZZ.33 H CMe₂CH₂SiMe₃ Me CF₂H ZZ.34 H CHMeCHMeSiMe₃ Me CF₂H ZZ.35 H CHMeCHMeSiMe₃ Me CF₃ ZZ.36 H CH₂CMe₂SiMe₃ Me CF₃ ZZ.37 H CH₂CMe₂SiMe₃ Me CF₂H ZZ.38 H CHMe(CH₂)₂SiMe₃ Me CF₂H ZZ.39 H CHMe(CH₂)₂SiMe₃ Me CF₃ ZZ.40 H (CH₂)₂SiMe₃ CH₂OMe CH₂Me ZZ.41 H (CH₂)₂SiMe₃ CH₂OCH₂Me CH₂Me ZZ.42 H SiMe₂CH₂CHMe₂ Me CF₃

Table 27 provides 42 compounds of formula (I-27) where R¹, R², R³ and R⁶ are as defined in Table 9.

Table 28 provides 42 compounds of formula (I-28) where R¹, R², R³ and R⁶ are as

Throughout this description, temperatures are given in degrees Celsius; “NMR” means nuclear magnetic resonance spectrum; MS stands for mass spectrum; “%” is percent by weight, unless corresponding concentrations are indicated in other units; “syn” refers to a syn configuration of the relevant substituent with respect to the annellated benzene ring; and “anti” refers to an anti configuration of the relevant substituent with respect to the anellated benzene ring.

The following abbreviations are used throughout this description:

-   -   m.p.=melting point b.p.=boiling point.     -   s=singlet br=broad     -   d=doublet dd=doublet of doublets     -   t=triplet q=quartet     -   m=multiplet ppm=parts per million

Table 29 shows selected melting point data for compounds of Tables 1 to 28.

TABLE 29 Compound No. m.p./(° C.)  1.03 56-57  1.13 176-177  1.15 liquid  1.50 64-66  2.005 146-147  2.017 148  2.029 148-149  2.067 165-166  2.070 139-142  2.219 94.6-95.4  2.273 125-126  2.321 124-125  2.411 117-118  2.427 103-105  2.423 105  2.445 (trans) 98-99  2.452 123-125  2.454 161-163  2.456 122-123  3.005 143-145  3.017 155-156  3.029 154-155  3.067 144-145  3.070 136-137  3.219 71-73  3.273 87-88  3.321 121-122  3.407 83-85  3.411 91-93  3.427 75-76  3.423 121-122  3.445 94-95  3.452 161-162  3.454 144-145  3.456 133-135  4.017 158-159  4.273 89-91  4.411 84-86  4.445 84-85  4.452 143-144  4.456 122-124  8.189 104-106  9.189 82-83 20.017 167-169 20.021 121-122 20.065 144-145 20.073 157-158 20.097 108-109 20.101 155-157 20.115 137-139 20.120 160-161 20.147 159-162 (decomposition) 20.148 133-139 20.149 amorphous 20.161 amorphous 20.166 (syn:anti 90:10) 150-153 20.166 (syn:anti 34:66) 111-116 20.168 (syn:anti 40:60) 102-120 20.169 (syn:anti 86:14) 105-109 20.170 (syn:anti 74:26) amorphous 20.171 (syn:anti 16:84) 106-107 20.171 (syn:anti 81:19) amorphous 20.176 (syn:anti 80:20) 126-129 20.179 187-189 20.180 109-110 21.097 107-109 21.101 120-122 21.017 175-177 21.021 125-126 21.065 114-116 21.073 135-137 21.105 140-143 21.114 189-191 21.115 164-166 21.120 172-175 21.148 134-136 21.152 170-172 21.153 amorphous 21.154 120-122 21.155 amorphous 21.161 amorphous 21.165(syn) 106-108 21.166 (syn:anti 90:10) 148-149 22.101 97-98 22.115 135-138 22.147 viscous 22.148 130-132 22.149 amorphous 22.161 amorphous 26.001 92-96 26.007 121-124 26.014 92-93 26.015 115-116 26.016 92-93 26.020 75-76 26.026 63-64 26.038 74-75 26.095 139-140 26.099 viscous 26.100 viscous 26.101 89-90 26.102 94-95 26.103 176-177 26.105 110-111 26.106 104-105 26.107 114-115 26.108 viscous 26.110 viscous 26.112 viscous 26.114 viscous 26.116 (syn:anti 86:14) waxy solid 26.116 (syn:anti 35:65) oil 26.118 (syn:anti 10:90) viscous 26.118 (syn:anti 82:18) viscous 26.119 oil 26.121 (syn:anti 50:50) oil 26.122 (syn:anti 84:14) oil 26.123 (syn:anti 75:25) 73-78 26.128 (syn:anti 74:26) oil 26.129 81-82 26.130 oil

The compounds according to formula (I) may be prepared according to the following reaction schemes.

(a) Preparation of a Compound of Formula (II).

Schemes 1, 2 and 3 demonstrate that a compound of formula E, H, K, L, N, O, P, R, S, T, U, V, W, Y or Z [where R¹ and R² are as defined above for formula (II); and R′ is C₁₋₅ alkyl] {each of which is a compound of formula (II), as defined above} may be prepared by a reaction sequence starting with a 1,2,3-triazole-4,5-dicarboxylic acid diester of formula A [Y. Tanaka et al., Tetrahedron, 29, 3271 (1973)] [where each R′ is, independently, C₁₋₅ alkyl] (preferably the dimethyl ester).

Treatment of A with an alkylating agent [such as R²-halo (where R² is as defined above for formula (II); and halo is preferably iodo) or an appropriate sulphate, sulphonate or carbonate ester] in the presence of a base [such as K₂CO₃, Na₂CO₃ or NEt₃] in a suitable solvent [such as acetonitrile, DMF or dimethylacetamide] at ambient to elevated temperatures furnishes a mixture of regioisomers, of formulae B and C, which may be separated by conventional methods. Saponification of a compound of formula B with up to one equivalent of a base [such as KOH, NaOH or LiOH] in a protic solvent [such as methanol], preferably under reflux conditions, provides a mono-ester of formula D. Subsequent reaction of a compound of formula D with a fluorinating agent [such as DAST (diethylamino sulphur trifluoride) or, preferably, SF₄] in the presence of hydrofluoric acid gives a 5-CF₃-1,2,3-triazole-4-carboxylic acid ester of formula E.

Alternatively, treatment of a compound of formula D with a chlorinating agent [such as thionyl chloride or phosgene] under standard conditions results in an acid chloride of formula F which may be reduced catalytically in an inert solvent [for example ethyl acetate or THF] in the presence of a base [for example Hünig base] to give an aldehyde-ester of formula G (modified Rosenmund conditions). Fluorination of a compound of formula G by means of DAST, dimethoxy-DAST or SF₄ in the presence of hydrofluoric acid, optionally with solvent, preferably at elevated temperatures, forms a 5-difluoromethyl-1,2,3-triazole-4-carboxylic acid ester of formula H.

Metal hydride reduction of a compound of formula G [for example by NaBH₄ or LiBH₄] in methanol provides a 5-hydroxymethyl-1,2,3-triazole of formula J, from which a 5-fluoromethyl derivative of formula K may be obtained by fluorination under mild conditions, preferably with DAST at low temperatures (0 to −78° C.) in an inert solvent [such as dichloromethane].

Alternatively, hydride reduction of a compound of formula J by conventional methods [for example via its mesylate, tosylate or iodide] results in a 5-methyl-1,2,3-triazole of formula L.

Chlorination of compound of formula D [for example by thionyl chloride] followed by treatment with ammonia, preferably in a protic solvent [such as water, methanol or ethanol] furnishes an amide of formula M from which a 5-cyano-1,2,3-triazole of formula N may be obtained by means of a dehydrating agent [such as phosphorylchloride].

Further transformations to prepare a compound of formula (II) [where R¹ and R² are as defined above for formula (I); Y is OR′ and R′ is C₁₋₅ alkyl] include a Hofmann rearrangement of an amide of formula M with NaOBr or NaOCl in the presence of NaOH to give a 5-amino-1,2,3-triazole of formula O.

Diazotation of a compound of formula O by means of sodium nitrite under aqueous acidic conditions [for example sulphuric acid] or with a nitrite ester [for example (i)-amyl nitrite] in an organic solvent [for example acetone, dichloromethane or THF] in the presence of a halogenide [such as CuCl or CuBr] gives a 5-halo-1,2,3-triazole of formula P [where halo is Cl or Br] which on treatment with a fluorinating agent [such as KF or CsF], preferably in DMF or N-methylpyrrolidone at elevated temperatures, results in a 5-fluoro-1,2,3-triazole of formula V.

By diazotation of a compound of formula O and subsequent acidic aqueous hydrolysis under heating, a 5-hydroxy-1,2,3-triazole of formula Q may be obtained. Treatment of a compound of formula Q with an alkylating agent [such as methyl iodide, dimethylsulphate or dimethylcarbonate] and a base [for example NaH, K₂CO₃ or Na₂CO₃] in a polar solvent [for example DMF, DMSO or CH₃CN] gives a 5-methoxy-1,2,3-triazole of formula R which may be converted to a trichloromethoxy derivative of formula S with a chlorinating agent [such as chlorine] in the presence of azoisobutyronitrile (AIBN) or ultra-violet irradiation at elevated temperature. By treatment of a compound of formula S with a fluorinating agent [for example KF or SbF₃] a 5-trifluoromethoxy-1,2,3-triazole of formula T may be prepared.

Oxidation of a compound of formula O with [for example sodium perborate] or treatment according to A. Sudalai et al. [Angew. Chem. Int. Ed. 40, 405 (2001)] leads to a 5-nitro derivative of formula U. Alternatively, a compound of formula U may also be obtained by treatment of a compound of formula P or V with NaNO₂ in an polar solvent [such as DMF, sulpholane or N-methylpyrrolidone] at elevated temperatures.

Transformations of a compound of formula (II′) [where R¹ and R² are as defined in formula (I); Y is OR′; and R′ is C₁₋₅ alkyl] to give a compound of formula (II) [where R¹ and R² are as defined in formula (I) and Y is halo or hydroxy] includes saponification with a base [such as KOH or NaOH] in a protic solvent [such as methanol, ethanol or water], at ambient or elevated temperature to give a 1,2,3-triazole-4-carboxylic acid of formula W. Chlorination of a compound of formula W under standard conditions [for example with thionyl chloride, phosgene or oxalyl chloride] yields an acid chloride of formula Y.

Fluorination of a compound of formula W with DAST or SF₄ under mild conditions [low to ambient temperatures], preferably in an inert solvent [such as dichloromethane] gives an acid fluoride of formula Z.

(b) Preparation of a Compound of Formula (III).

A compound of formula (III)

H₂N-A  (III)

where A is as defined above for a compound of formula (I), is useful as an intermediate in the preparation of a compound of formula (I).

Most o-substituted amino-aryls and amino-heteroaryls of formula (III) are known from the literature, but some are novel.

A compound of formula (IIIa) may be obtained according to scheme 4:

Treatment of an ortho-substituted nitrobenzonorbornadiene of formula AA (where R¹³, R¹⁴, R¹⁵, R¹⁶ and X are as defined above for a compound of formula (I)) [obtained through Diels-Alder addition of an in situ generated benzyne, for example, starting from a 6-nitroanthranilic acid as described by L. Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitable benzyne precursers (see H. Pellissier et al. Tetrahedron, 59, 701 (2003) with a 5-7 membered cyclic 1,4-diene according to, or by analogy to, L. Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), D. Gravel et al. Can. J. Chem. 69, 1193 (1991), J. R. Malpass et al. Tetrahedron, 48, 861 (1992), D. E. Lewis et al. Synthetic Communications, 23, 993 (1993), R. N. Warrener et al. Molecules, 6, 353 (2001), R. N. Warrener et al. Molecules, 6, 194 (2001) or I. Fleming et al. J. Chem. Soc., Perkin Trans. 1, 2645 (1998)] with Zn, in the presence of ammonium chloride or an aluminium amalgam, in a protic solvent [such ethanol or water] gives an aniline of formula CC, whilst catalytic hydrogenation of a compound of formula AA with, for example, RaNi, Pd/C or Rh/C in the presence of a solvent [for example THF, ethyl acetate, methanol or ethanol] affords an aniline of formula BB.

Compounds of Formula (IIIb)

where R⁶ is an aliphatic or alicyclic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms] and R⁷⁻¹⁰ are as defined in formula (I) may be prepared by analogy with literature examples. References include e.g. E. A. Chemyshew et al., Bull. Acad. Sci. USSR, 1960, 1323; K. T. Kang et al., Tetrahedron Letters, 32, 4341 (1991), Synthetic Comm., 24, 1507 (1994); M. Murata et al., Tetrahedron Letters 40, 9255 (1999); A. Falcou et al., Tetrahedron 56, 225 (2000); A. Arcadi et al., Tetrahedron Letters 27, 6397 (1986); K. C. Nicolaou et al., Chem. Eur. J. 1, 318 (1995); N. Chatani et al., J. Org. Chem. 60, 834 (1995); T. Stuedemann et al., Tetrahedron 54, 1299 (1998); P. F. Hurdlik et al., J. Org. Chem. 54, 5613 (1989); K. Karabelas et al., J. Org. Chem. 51, 5286 (1986); T. Jeffery, Tetrahedron Letters 40, 1673 (1999) and Tetrahedron Letters 41, 8445 (2000); K. Olofson et al., J. Org. Chem. 63, 5076 (1998); H. Uirata et al., Bull. Chem. Soc. Jap. 57, 607 (1984); and G. Maas et al., Tetrahedron 49, 881 (1983); and references cited therein.

Recent reviews for the introduction of Si-containing functionalities into phenyl derivatives can be found in “The Chemistry of Organosilicon Compounds”, Vols. 1-3, S. Patai, Z. Rappaport and Z. Rappaport, Y. Apeloid eds., Wiley 1989, 1998, 2001 and “Houben-Weyl Science and Synthesis”, Organometallics Vol. 4, I. Fleming ed., G. Thieme 2002.

Another group of anilines comprises compounds of formula (IIIc)

where R′ represents C₂₋₄ alkyl, C₂₋₄ haloalkyl or C₃₋₆ cycloalkyl (itself optionally substituted by up to 3 substituents, independently selected from halo, C₁₋₃ alkyl, C₁₋₃ haloalkyl and C₁₋₄ haloalkoxy).

A compound of formula (IIIc) may be prepared by a reaction sequence starting with a crossed aldol condensation of benzaldehyde with a ketone of formula CH₃C(O)R′ [where R′ is as defined above for a compound of formula (IIIc)] in the presence of NaOH or KOH in a solvent (such as water or ethanol) and usually under reflux conditions or alternatively by reaction of benzaldehyde with a Wittig reagent under standard conditions. The resulting α,β-unsaturated ketone of formula (IV) [where R′ is as defined above for a compound (IIIc)]:

may then be converted into a compound of formula (V′) [where R′ is as defined above for a compound (IIIc)]:

by reacting first with hydrazine hydrate in ethanol under reflux conditions and then heating (in the range of from 150 to 250° C.) in the presence of KOH (distilling off the solvent). After nitration with HNO₃—H₂O or HNO₃-acetic anhydride in a cooled vessel (in the range of from −30° C. to 0° C.), the resulting o/p-mixture of a nitrobenzene of formula (VI) [where R′ is as defined above for a compound (IIIc)]:

may then be separated and catalytically reduced (Pt/C/H₂ or Ra—Ni/H₂) in a solvent (such as methanol, ethanol of THF) at ambient temperature to give a compound of formula (IIIc).

Alternatively the synthesis of a compound of formula (IIId) [where R′^(a) is hydrogen or methyl]

may be accomplished by a reaction sequence started by a Wittig reaction of o-nitrobenzaldehyde with an ylide, prepared from a cyclopropylmethyltriphenylphosphonium bromide in the presence of a strong base [such as NaH] in a solvent [such as DMSO], in the range of 0-85° C. The resulting E/Z-mixture of a compound of formula (VII)

[where R′^(a) is hydrogen or methyl] may be converted to a compound of formula (VIII)

by the application of the Simmons Smith reaction (Zn—Cu, CH₂I₂, ether as a solvent) to the olefin group of a compound of formula (VII) to give a compound of formula (VIII). The reduction of the nitro moiety of a compound of formula (VIII) to give a compound of formula (IIIc) may be performed by using the same conditions as described above for a compound of formula (VI).

(c) Preparation of a Compound of Formula (I).

A compound of formula (I) [where A, R¹ and R² are as defined above and R³ is H] may be synthesized by reacting a compound of formula (II′) [where R¹ and R² are as defined above and R′ is C₁₋₅ alkyl] with an aniline of formula (III) [where A is as defined above for a compound of formula (I)] in the presence of NaN(TMS)₂ at −10° C. to ambient temperature, preferably in dry THF, as described by J. Wang et al., Synlett, 2001, 1485.

Alternatively, a compound of formula (I) [where A, R¹ and R² are as defined above and R³ is H] may be prepared by reacting a compound of formula (II) [where R¹ and R² are as defined above and Y is OH] with a compound of formula (III) [where A is as defined above for a compound of formula (I)] in the presence of an activating agent [such as BOP-Cl] and two equivalents of a base [such as NEt₃] or by reacting a compound of formula (II) [where Y is Cl, Br or F] with a compound of formula (III) in the presence of one equivalent of a base [such as NEt₃, NaHCO₃, KHCO₃, Na₂CO₃ or K₂CO₃] in a solvent [such as dichloromethane, ethyl acetate or DMF] preferably at −10 to 30° C.

A compound of formula (I) [where R³ is as defined above for formula (I), except that it is not hydrogen] may be prepared by reacting a compound of formula (I) [where R³ is hydrogen] with a species Y—R³ [where R³ is as defined for formula (I), except that it is not hydrogen; and Y is halogen, preferably Cl, Br or I; or Y is such that Y—R³ is an anhydride: that is, when R³ is COR*, Y is OCOR*] in the presence of a base [for example NaH, NEt₃, NaHCO₃ or K₂CO₃] in an appropriate solvent [such as ethyl acetate] or in a biphasic mixture [such as dichloromethane/water mixturte], at −10 to 30° C.

Surprisingly, it has now been found that the novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.

The compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, for example from phytopathogenic microorganisms.

It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

Furthermore the compounds according to present invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management, etc.

The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).

Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO97/33890.

The compounds of formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

A preferred method of applying a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation [that is, a composition containing the compound of formula (I)] and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.

Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seed drenching agent, convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The following non-limiting Examples illustrate the above-described invention in more detail.

EXAMPLE 1

This Example illustrates the preparation of Compound No. 1.15 [2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester] and Compound No. 1.13 [2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid].

a) Preparation of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic acid dimethylester and 1-methyl-1H-1,2,3-triazole-4,5-dicarboxylic acid dimethylester

1,2,3-Triazole-4,5-dicarboxylic acid dimethyl ester (Y. Tanaka et al. Tetrahedron 29, 3271 (1973)) (74.06 g; 0.40 mol), potassium carbonate (110.57 g; 0.80 mol) and methyl iodide (73.81 g; 0.52 mol) were reacted in acetonitrile (1000 ml) at 40° C. for 20 minutes and then for 20 hours at ambient temperature. The mixture was poured onto ice-water and extracted with ether to give the crude product (70.66 g) as a mixture of isomers. Separation on silica gel in ethyl acetate-hexane (2:3) yielded 36.51 g (46%) of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic acid dimethylester [m.p. 86-87° C.; ¹H-NMR (300 MHz, DMSO-d₆), δ (ppm): 4.27 (s, 3H), 3.88 (s, 6H)] and 26.92 g (34%) of 1-methyl-1H-1,2,3-triazole-4,5-dicarboxylic dimethylester [m.p. 63-64° C.; ¹H-NMR (300 MHz, DMSO-d₆), δ (ppm): 4.19 (s, 3H), 3.93 (s, 3H), 3.87 (s, 3H)].

b) Preparation of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic acid monomethyl ester

To a solution of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic acid dimethylester (1.2 g; 6 mmol) in 30 ml methanol was added 358 mg KOH (assay 86%; 5.5 mmol). The mixture was heated at reflux temperature for 48 hours. The solvent was evaporated and the residue was then taken into water and extracted with ethyl acetate (3 times). The combined organic phases contained non-reacted starting material. The aqueous phase was acidified with 2N HCl (pH2-3) and extracted with ethyl acetate (3 times). The extracts were combined, dried (anhydrous MgSO₄) and evaporated to dryness to give 803 mg (72%) of the desired compound (m.p. 125-126° C.; ¹H-NMR (300 MHz, DMSO-d₆), δ (ppm): 13.7 (br.s, 1H, exchangable with D₂O), 4.24 (s, 3H), 3.84 (s, 3H).

c) Preparation of 2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester [Compound Number 1.15]

2-Methyl-2H-1,2,3-triazole-4,5-dicarboxylic acid monomethyl ester (2.9 g; 15.66 mmol) and dichloromethane (160 ml) were placed in an 0.3 litre monel autoclave. Under an inert atmosphere and cooling with dry ice, gaseous HF (27 g) was introduced at −50° C. followed by gaseous SF₄ (distilled, 6.9 g; 64.23 mmol). The autoclave was heated to 80° C. for 6 hours. The maximum pressure amounted 9.8 bar. After cooling to ambient temperature the reaction mixture was poured onto ice-dichloromethane and adjusted to pH7 with aqueous NaHCO₃. Extraction with dichloromethane (3 times), drying over Na₂SO₄ and evaporation under reduced pressure afforded the crude product. Purification by Kugelrohr-distillation at 3 mbar and ca. 180° C. gave 2.8 g (85%) of Compound No. 1.15 as a yellowish liquid.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 4.29 (s, 3H), 3.97 (s, 3H);

¹⁹F-NMR (235 MHz, CDCl₃), δ (ppm): −61.7.

¹³C-NMR (125 MHz, CDCl₃), □ δ (ppm): 159.05, 139.65 (q, J_(C(5)F)=40.8 Hz), 137.20, 119.63 (q, J_(CF)=269.4 Hz, CF₃), 52.96, 43.01.

d) Preparation of 2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid [Compound Number 1.13]

A solution of 2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester [Compound Number 1.15] (2.09 g; 0.01 mol) and KOH (86%; 0.783 g; 1.2 eq.) in THF (50 ml) was heated at reflux temperature for 3.5 hours. The solution was evaporated, the residue was dissolved in water and acidified to pH 1-2 with HCl (1M). Evaporation of the aqueous solution followed by continuous extration in ethylacetate for 20 hours gave of Compound No 1.13 (2.11 g; 100%) as a crystalline solid.

¹H-NMR (400 MHz, DMSO-d₆), δ (ppm): 4.19 (s, 3H).

¹⁹F-NMR (235 MHz, DMSO-d₆), δ (ppm): −59.3.

¹³C-NMR (125 MHz, DMSO-d₆), □ δ (ppm): 160.74, 144.08, 135.81 (q, J_(C(5)F)=38.1 Hz), 120.63 (q, J_(CF)=268.4 Hz, CF₃), 42.20.

EXAMPLE 2

This Example illustrates the preparation of Compound No. 1.03 [2-methyl-5-difluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methyl ester].

a) Preparation of 5-Chlorocarbonyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester

Methyl 2-methyl-1,2,3-triazole-4,5-dicarboxylate (2.3 g; 0.011 mol) was reacted with oxalyl chloride (1.46 ml; 0.014 mol) plus two drops of DMF in dichloromethane (20 ml) at 20° C. When the vigourous reaction ceased the temperature was raised to reflux for 15 hours. The mixture was evaporated to dryness to give 2.7 g of the acid chloride as a solid. ¹H-NMR (300 MHz, CDCl₃), δ (ppm): 4.48 (s, H), 4.0 (s, 3H).

b) Preparation of 5-formyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester

To a solution of freshly prepared 5-Chlorocarbonyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester (2.7 g; ca. 13 mmol) in THF (270 ml) was added ethyl-diisopropyl-amine (1.88 g; 1.1 eq.). The mixture was hydrogenated in the presence of 2.7 g 10% Pd/C at 0-5° C. at normal pressure for 2½ hours and subsequently filtered from the catalyst. The clear solution was evaporated to give the crude as a solid which was dissolved again in ethyl acetate and stirred for a couple of minutes with silica gel. After filtration and evaporation 1.77 g (84%) of pure product as off-white crystals were obtained [m.p. 107-108° C.; ¹H-NMR (300 MHz, CDCl₃), δ (ppm): 10.43 (s, 1H), 4.33 (s, 3H), 4.01 (s, 3H)].

c) Preparation of 2-methyl-5-difluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methyl ester. [Compound No. 1.03.]

5-Formyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester (600 mg; 3.5 mmol) in 0.5 ml CHCl₃ were reacted with (bis(2-methoxyethyl)amino) sulfurtrifluoride (1350 mg; 6.1 mmol) at ambient temperature to 50° C. for 6 days. The resulting orange solution was carefully quenched with 6 ml of a saturated aqueous NaHCO₃ solution (vigorous reaction) and extracted with ethyl acetate (twice). The combined organic phases were washed with aqueous NaHCO₃-solution, dried over anhydrous MgSO₄ and evaporated to give 351 mg (52%) of colourless crystals.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 7.15 (t, J_(HF)=53.5 Hz, 1H, H—CF₂), 4.30 (s, 3H), 3.98 (s, 3H); ¹⁹F-NMR (235 MHz, CDCl₃), δ (ppm): −116.1; ¹³C-NMR (125 MHz, CDCl₃), δ (ppm): 160.0, 143.6 (t, J_(C(5)F)=25.6 Hz), 137.2, 108.0 (t, J_((CF))=237.8 Hz, CHF₂), 52.6, 42.7].

EXAMPLE 3

This Example illustrates the preparation of Compound No. 1.50 [2-methyl-5-fluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methyl ester].

a) Preparation of 5-hydroxymethyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester

2.6 g (13.3 mmol) of 5-formyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester (see Example 2a) in methanol (100 ml) was treated with NaBH₄ (601 mg) under stirring for 1 hour at ambient temperature. The reaction mixture was quenched with saturated aqueous ammonium chloride solution, extracted with ethyl acetate, dried with Na₂SO₄ and evaporated to give the crude as an oil. Purification on silica gel in ethyl acetate:hexane (2:1) yielded 1.85 g (81%) of the crystalline product, m.p. 112-113° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 4.86 (d, J=6.9 Hz, 1H), 4.22 (s, 3H), 3.98 (s, 3H), 3.53 (t; J=6.9 Hz, exchangeable with D₂O).

b) Preparation of 2-methyl-5-fluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methyl ester. [Compound No. 1.50.]

A solution of 5-hydroxymethyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester (200 mg; 1.1 mmol) in CH₂Cl₂ (15 ml) was reacted with 0.26 ml diethylamino sulfur trifluoride (2 mmol) for 15 minutes at −40° C. followed by 15 hours at ambient temperature. After evaporation, the crude product was purified on silica gel in ethyl acetate:hexane (3:1) to give 181 mg (95%) of the desired product, m.p. 64-66° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 5.66 (d, J_(HF)=47.5 Hz, 2H, H₂—CF), 4.26 (s, 3H), 3.96 (s, 3H).

¹⁹F-NMR (235 MHz, CDCl₃), δ (ppm): −214.

¹³C-NMR (125 MHz, CDCl₃), δ (ppm): 161.6, 145.86 (d, J_(C(5)F)=18.7 Hz), 137.09, 74.82 (d, J_(CF)=166.6 Hz, CH₂F), 52.2, 42.3.

EXAMPLE 4

This Example illustrates the preparation of Compound No. 3.017 [5-difluoromethyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid (4-chloro-biphenyl-2-yl)-amide].

To a solution of 2-methyl-5-difluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methyl ester (300 mg; 1.57 mmol) and 4′-chloro-biphenyl-2-ylamine (320 mg; 1.57 mmol) in THF (3 ml) was added sodium bis(trimethylsilyl)-amide (0.88 ml 2M in THF; 1.76 mmol; 1.12 eq.) by syringe at 0° C. over 1.5 minutes. The reaction mixture was stirred at 0° C. for 15 minutes and then at ambient temperature for 22 hours. It was then poured on cold saturated NH₄Cl solution and extracted with ethyl acetate. After washing with brine it was dried (anhydrous MgSO₄) and evaporated to dryness to give a solid, which was triturated with hexane. The colourless crystalline product was filtered and dried: 300 mg (53%) [m.p. 155-156° C.; ¹H-NMR (300 MHz, CDCl₃), δ (ppm): 8.5 (br, exchangeable with D₂O, 1H), 8.4 (d, 1H), 7.5-7.2 (m, 7H), 7.38 (t, J_(HF)=52.5 Hz, 1H, CHF₂), 4.2 (s, 3H), LC-MS: 363 (M+H)].

EXAMPLE 5

This Example illustrates the preparation of Compound No. 2.219 [2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid [2-(1,3-dimethyl-butyl)-phenyl]-amide].

To a solution of 2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester (150 mg; 0.75 mmol) and 2-(1,3-dimethyl-butyl)-phenylamine (133 mg; 0.75 mmol) in 1.5 ml THF was added sodium bis(trimethylsilyl)-amide (0.638 ml 2M in THF; 1.7 eq.) by syringe at ambient temperature. The reaction mixture was stirred for 20 hours and was then poured on cold saturated NH₄Cl solution and extracted with ethyl acetate. After washing with brine it was dried (anhydrous MgSO₄) and evaporated to dryness to give the crude product, which was purified on silica gel in cyclohexane-ethyl acetate (18:1) The crystalline product was triturated in hexane, filtered and dried in vacuo to yield 130 mg (49%) of Compound No. 2.219 [mp 94.6-95.4° C.; ¹H-NMR (300 MHz, CDCl₃), δ (ppm): 8.5 (br.s, exchangeable with D₂O, 1H), 8.0 (d, 1H), 7.3-7.15 (m, 3H), 4.33 (s, 3H), 3.0 (m, 1H), 1.55-1.35 (m, 3H), 1.26 (d, 3H), 0.9 (2d, 6H); LC-MS: 355.6 (M+H)].

EXAMPLE 6

This Example illustrates the preparation of Compound No. 26.014 [1,8-Dimethyl-[1-oxa-tricyclo[6.2.1.0*2.7*]undeca-2,4,6-trien-3-yl-amine].

A solution of 1,4-dimethyl-5-nitro-1,4-dihydro-1,4-epoxynaphthalene (5.49 g; 25.27 mmol) (see T. Nishiyama et al., Rikagaku-hen, 28, 37-43 (2000)) in 55 ml THF was hydrogenated in the presence of RaNi (1.1 g) at ambient temperature. Hydrogen uptake was 2.23 litre (97%) after 18 hours. After filtering off the catalyst, the filtrate was evaporated and taken into ether, washed with aqueous NaHCO₃-solution and dried (NaSO₄) to give 4.60 g of crude product, as an oil. Trituration with hexane and a trace of ether furnished a total of 4.5 g (94%) of reddish crystalline product, m.p. 92-93° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 7.05 (t, 1H), 6.7 (t, 2H), ca. 5 (br., exchangeable with D₂O, 2H), 2.0 (s, 3H), 1.9 (m, 2H), 1.8 (s, 3H), 1.7 (m, 1H), 1.5 (m, 1H).

EXAMPLE 7

This Example illustrates the preparation of Compound No. 26.001 [1,8-Dimethyl-11-oxa-tricyclo[6.2.1.0*2.7*]undeca-2,4,6,9-tetraen-3-yl-amine].

To 1,4-dimethyl-5-nitro-1,4-dihydro-1,4-epoxynaphthalene (4.22 g; 19.43 mmol) (see Example 6) in ethanol (60 ml) was added a solution of ammoniumchloride (2.08 g) in H₂O (5.2 ml) at 47° C. Under vigorous stirring, zinc powder (9.10 g; 0.14 mol) was added in portions over a period of 5 minutes. The suspension was heated to reflux for 5½ hours followed by filtration through Hyflo™ to give a clear yellow filtrate. After evaporation, the crude product amounted 4.57 g, as a viscous oil. Column chromatography on silica gel in ethyl acetate-hexane (1:4) gave 1.24 g (34%) of the desired product, as brownish crystals, m.p. 92-96° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 6.85 and 6.7 (two m, 2×2H), 6.47 (t, 1H), ca. 5-3 (br., exchangeable with D₂O, 2H), 2.07 (s, 3H), 1.85 (s, 3H).

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I)

Working procedures for preparing formulations of the compounds of formula I such as Emulsifiable Concentrates, Solutions, Granules, Dusts and Wettable Powders are described in WO97/33890.

BIOLOGICAL EXAMPLES Fungicidal Actions

Example B-1

Action Against Puccinia recondita/Wheat (Brownrust on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (1×10⁵ uredospores/ml) on the test plants. After an incubation period of 2 days at 20° C. and 95% r.h. the plants are kept in a greenhouse for 8 days at 20° C. and 60% r.h. The disease incidence is assessed 10 days after inoculation.

Infestation is prevented virtually completely (0-5% infestation) with each of Compounds 2.273, 3.219, 3.273, 3.321, 8.189, 9.189, 20.017, 20.022, 21.017 and 21.022.

Example B-2 Action Against Podosphaera leucotricha/Apple (Powdery Mildew on Apple)

5 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22° C. and 60% r.h. under a light regime of 14/10 hours (light/dark) the disease incidence is assessed.

Compounds 2.005, 3.017, 3.219 and 9.189 each exhibit strong efficacy (<20% infestation).

Example B-3 Action Against Venturia inaequalis/Apple (Scab on Apple)

4 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% r.h. the plants are placed for 4 days at 21° C. and 60% r.h. in a greenhouse. After another 4 day incubation period at 21° C. and 95% r.h. the disease incidence is assessed.

Compounds 3.017, 3.219 and 9.189 each exhibit strong efficacy (<20% infestation).

Example B-4 Action Against Erysiphe graminis/Barley (Powdery Mildew on Barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20° C./18° C. (day/night) and 60% r.h. in a greenhouse the disease incidence is assessed.

Compounds 2.017, 2.029, 2.273, 3.005, 3.017, 3.029, 3.067, 3.070, 3.219, 3.273, 3.321, 3.407, 8.189, 9.189 and 21.017 each exhibit strong efficacy (<20% infestation).

Example B-5 Action Against Botrytis cinerea/Grape (Botrytis on Grapes)

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (1×10⁶ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% r.h. in a greenhouse the disease incidence is assessed.

Compounds 2.029, 3.017 and 3.219 each show good activity in this test (<50% disease incidence).

Example B-6 Action Against Botrytis cinerea/Tomato (Botrytis on Tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (1×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% r.h. in a growth chamber the disease incidence is assessed.

Compounds 2.029, 3.005, 3.029, 3.067, 3.070, 3.219, 3.273, 9.189 and 20.017 each exhibit good efficacy (<50% disease incidence).

Example B-7 Action Against Septoria nodorum/Wheat (Septoria Leaf Spot on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5×10⁵ conidia/ml) on the test plants. After an incubation period of 1 day at 20° C. and 95% r.h. the plants are kept for 10 days at 20° C. and 60% r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation.

Compounds 3.273 and 9.189 each show good activity in this test (<50% disease incidence).

Example B-8 Action Against Helminthosporium teres/Barley (Net Blotch on Barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3×10⁴ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% r.h. in a greenhouse the disease incidence is assessed.

Compounds 2.005, 2.017, 2.029, 2.067, 2.070, 2.273, 3.005, 3.017, 3.029, 3.067, 3.070, 3.219, 3.407, 9.189 and 21.017 each show good activity in this test (<20% disease incidence).

Example B-9 Action Against Alternaria solani/Tomato (Early Blight on Tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2×10⁵ conidia/ml) on the test plants. After an incubation period of 3 days at 20° C. and 95% r.h. in a growth chamber the disease incidence is assessed.

Compounds 2.005, 2.029, 3.005, 3.017, 3.029 and 9.189 each show good activity in this test (<20% disease incidence).

Example B-10 Action Against Uncinula necator/Grape (Powdery Mildew on Grapes)

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 26° C. and 60% r.h. under a light regime of 14/10 hours (light/dark) the disease incidence is assessed.

Compounds 3.017, 3.219 and 9.189 each show good activity in this test (<20% disease incidence). 

1-5. (canceled)
 6. A compound of formula (II):

where R¹ and R² are as defined in claim 1 and Y is halogen, hydroxy or C₁₋₅ alkoxy; provided that when R¹ is chloro and R² is 4-CH₃O—C₆H₄—CH₂—, Y is not C₂H₅O; when R¹ is CH₃O and R² is CH₃, Y is not C₂H₅O; when R¹ is bromo and R² is CH₃OCH₂, Y is not CH₃O; and when R¹ is CH₃ and R² is C₂H₅, Y is not OH.
 7. A compound of formula (IIIa)

where R¹³, R¹⁴, R¹⁵, R¹⁶, X and Q are as defined in claim 1; provided that when R¹³, R¹⁴, R¹⁵ and R¹⁶ are each H then X is not CH₂ when Q is a double bond and X is not CH₂CH₂ when Q is a single bond or a double bond; and when R¹³ is CH₃, R¹⁴ is OCH₃ and R¹⁵ and R¹⁶ are both H then X is not CH₂CH₂ when Q is a single bond. 8-9. (canceled) 